Use of metal complex compounds as oxidation catalysts

ABSTRACT

Use of metal complex compounds of formula 
       [L n Me m X p ] z Y q ,   (1)     wherein Me is manganese, titanium, iron, cobalt, nickel or copper,   X is a coordinating or bridging radical,   n and m are each independently of the other an integer having a value of from 1 to 8,   p is an integer having a value of from 0 to 32,   z is the charge of the metal complex,   Y is a counter-ion,   q=z/(charge Y), and   L is a ligand of formula   
     
       
         
         
             
             
         
       
         
         wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10  and R 11  are each independently of the others hydrogen; unsubstituted or substituted C 1 -C 18 alkyl or aryl; cyano; halogen; nitro; —COOR 12  or —SO 3 R 12  wherein R 12  is in each case hydrogen, a cation or unsubstituted or substituted C 1 -C 18 alkyl or aryl; —SR 13 , —SO 2 R 13  or —OR 13  wherein R 13  is in each case hydrogen or unsubstituted or substituted C 1 -C 18 alkyl or aryl; —N(R 13 )—NR′ 13 R″ 13  wherein R 13 , R′ 13  and R″ 13  are as defined above for R 13 ; —NR 14 R 15  or —N ⊕ R 14 R 15 R 16  wherein R 14 , R 15  and R 16  are each independently of the other(s) hydrogen or unsubstituted or substituted C 1 -C 18 alkyl or aryl, or R 14  and R 15  together with the nitrogen atom bonding them form an unsubstituted or substituted 5-, 6- or 7-membered ring which may optionally contain further hetero atoms; 
         with the proviso that R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10  and R 11  are not simultaneously hydrogen, as catalysts for oxidation reactions, 
         and the novel metal complex compounds of formula (1) and the novel ligands of formula (2).

This application is a divisional of application Ser. No. 11/497,444,pending, which is a divisional of application Ser. No. 10/476,043, nowU.S. Pat. No. 7,161,005, which is the National Stage of InternationalApplication PCT/EP02/04572, filed Apr. 25, 2002, all of which are hereinincorporated by reference.

The present invention relates to the use of metal complex compounds withterpyridine ligands as oxidation catalysts. The present inventionrelates also to formulations comprising such metal complex compounds, tonovel metal complex compounds and to novel ligands.

The metal complex compounds are used especially for improving the actionof peroxides, for example in the treatment of textile material, withoutat the same time causing any appreciable damage to fibres and dyeings.

Peroxide-containing bleaching agents have been used in washing andcleaning processes for some time. They have an excellent action at aliquor temperature of 90° C. and above, but their performance noticeablydecreases with lower temperatures. It is known that various transitionmetal ions, added in the form of suitable salts, or coordinationcompounds containing such cations catalyse the decomposition of H₂O₂. Inthat way it is possible to increase the bleaching action of H₂O₂, or ofprecursors that release H₂O₂, or of other peroxo compounds, thebleaching action of which is unsatisfactory at lower temperatures.Particularly significant for practical purposes are those combinationsof transition metal ions and ligands the peroxide activation of which ismanifested in an increased tendency towards oxidation in respect ofsubstrates and not only in a catalase-like disproportionation. Thelatter activation, which tends rather to be undesirable in the presentcase, could impair the bleaching effects of H₂O₂ and its derivativeswhich are insufficient at low temperatures.

In respect of H₂O₂ activation having effective bleaching action,mononuclear and polynuclear variants of manganese complexes with variousligands, especially with 1,4,7-trimethyl-1,4,7-triazacyclononane andoptionally oxygen-containing bridge ligands, are currently regarded asbeing especially effective. Such catalysts have adequate stability underpractical conditions and, with Mn^(n+), contain an ecologicallyacceptable metal cation, but their use is unfortunately associated withconsiderable damage to dyes and fibres.

The aim of the present invention was, therefore, to provide improvedmetal complex catalysts for oxidation processes which fulfil the abovedemands and, especially, improve the action of peroxy compounds in anextremely wide range of fields of use without giving rise to anyappreciable damage.

The invention accordingly relates to the use of metal complex compoundsof formula

[L_(n)Me_(m)X_(p)]^(z)Y_(q)  (1),

wherein Me is manganese, titanium, iron, cobalt, nickel or copper,X is a coordinating or bridging radical,n and m are each independently of the other an integer having a value offrom 1 to 8,p is an integer having a value of from 0 to 32,z is the charge of the metal complex,Y is a counter-ion,q=z/(charge Y), andL is a ligand of formula

whereinR₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are each independentlyof the others hydrogen; unsubstituted or substituted C₁-C₁₈alkyl oraryl; cyano; halogen; nitro; —COOR₁₂ or —SO₃R₁₂ wherein R₁₂ is in eachcase hydrogen, a cation or unsubstituted or substituted C₁-C₁₈alkyl oraryl; —SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in each case hydrogen orunsubstituted or substituted C₁-C₁₈alkyl or aryl; —N(R₁₃)—NR′₁₃R″₁₃wherein R₁₃, R′₁₃ and R″₁₃ are as defined above for R₁₃; —NR₁₄R₁₅ or—N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are each independently of theother(s) hydrogen or unsubstituted or substituted C₁-C₁₈alkyl or aryl,or R₁₄ and R₁₅ together with the nitrogen atom bonding them form anunsubstituted or substituted 5-, 6- or 7-membered ring which mayoptionally contain further hetero atoms;with the proviso that R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ and R₁₁are not simultaneously hydrogen,as catalysts for oxidation reactions.

The mentioned C₁-C₁₈alkyl radicals are generally, for example,straight-chain or branched alkyl radicals, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl orstraight-chain or branched pentyl, hexyl, heptyl or octyl. Preference isgiven to C₁-C₁₂alkyl radicals, especially C₁-C₈alkyl radicals and moreespecially C₁-C₄alkyl radicals. The mentioned alkyl radicals can beunsubstituted or substituted e.g. by hydroxyl, C₁-C₄alkoxy, sulfo or bysulfato, especially by hydroxyl. The corresponding unsubstituted alkylradicals are preferred. Very special preference is given to methyl andethyl, especially methyl.

Examples of aryl radicals that generally come into consideration arephenyl or naphthyl unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl, sulfo, hydroxyl, amino,N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or substituted byhydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, phenyl,phenoxy or by naphthoxy. Preferred substituents are C₁-C₄alkyl,C₁-C₄alkoxy, phenyl and hydroxy. Special preference is given to thecorresponding phenyl radicals.

Halogen is generally especially chlorine, bromine or fluorine, specialpreference being given to chlorine.

Examples of cations that generally come into consideration are alkalimetal cations, such as lithium, potassium and especially sodium,alkaline earth metal cations, such as magnesium and calcium, andammonium cations. The corresponding alkali metal cations, especiallysodium, are preferred.

Suitable metal ions for Me are e.g. manganese in oxidation states II-V,titanium in oxidation states III and IV, iron in oxidation states I toIV, cobalt in oxidation states I to III, nickel in oxidation states I toIII and copper in oxidation states I to III, with special preferencebeing given to manganese, especially manganese in oxidation states II toIV, preferably in oxidation state II. Also of interest are titanium IV,iron II-IV, cobalt II-III, nickel II-III and copper II-III, especiallyiron II-IV.

For the radical X there come into consideration, for example, CH₃CN,H₂O, F⁻, Cl⁻, Br⁻, HOO⁻, O₂ ⁻, O²⁻, R₁₇COO⁻, R₁₇O⁻, LMeO⁻ and LMeOO⁻,wherein R₁₇ is hydrogen or unsubstituted or substituted C₁-C₁₈alkyl oraryl, and C₁-C₁₈alkyl, aryl, L and Me have the definitions and preferredmeanings given hereinabove and hereinbelow. R₁₇ is especially hydrogen,C₁-C₄alkyl or phenyl, more especially hydrogen.

As counter-ion Y there come into consideration, for example, R₁₇COO⁻,ClO₄ ⁻, BF₄ ⁻, PF₆ ⁻, R₁₇SO₃ ⁻, R₁₇SO₄ ⁻, SO₄ ²⁻, NO₃ ⁻, F⁻, Cl⁻, Br⁻and I⁻, wherein R₁₇ is hydrogen or unsubstituted or substitutedC₁-C₁₈alkyl or aryl. R₁₇ as C₁-C₁₈alkyl or aryl has the definitions andpreferred meanings given hereinabove and hereinbelow. R₁₇ is especiallyhydrogen, C₁-C₄alkyl or phenyl, more especially hydrogen. The charge ofthe counter-ion Y is accordingly preferably 1- or 2-, especially 1-.

n is preferably an integer having a value of from 1 to 4, preferably 1or 2 and especially 1.

m is preferably an integer having a value of 1 or 2, especially 1.

p is preferably an integer having a value of from 0 to 4, especially 2.

z is preferably an integer having a value of from 8− to 8+, especiallyfrom 4− to 4+ and more especially from 0 to 4+. z is more especially thenumber 0.

q is preferably an integer from 0 to 8, especially from 0 to 4 and ismore especially the number 0.

R₁₂ is preferably hydrogen, a cation, C₁-C₁₂alkyl, or phenylunsubstituted or substituted as indicated above. R₁₂ is especiallyhydrogen, an alkali metal cation, alkaline earth metal cation orammonium cation, C₁-C₄alkyl or phenyl, more especially hydrogen or analkali metal cation, alkaline earth metal cation or ammonium cation.

R₁₃, R′₁₃ and R″₁₃ are preferably hydrogen, C₁-C₁₂alkyl, or phenylunsubstituted or substituted as indicated above. R₁₃, R″₁₃ and R″₁₃ areespecially hydrogen, C₁-C₄alkyl or phenyl, more especially hydrogen orC₁-C₄alkyl, preferably hydrogen. Examples of the radical of the formula—N(R₁₃)—NR′₁₃R″₁₃ that may be mentioned include —N(CH₃)—NH₂ andespecially —NH—NH₂. Examples of the radical of the formula —OR₁₃ thatmay be mentioned include hydroxyl and C₁-C₄alkoxy, such as methoxy andespecially ethoxy.

When R₁₄ and R₁₅ together with the nitrogen atom bonding them form a 5-,6- or 7-membered ring it is preferably an unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring. The piperazine ring can be substituted by C₁-C₄alkyle.g. at the nitrogen atom not bonded to the phenyl radical. In addition,R₁₄, R₁₅ and R₁₆ are preferably hydrogen, unsubstituted orhydroxyl-substituted C₁-C₁₂alkyl, or phenyl unsubstituted or substitutedas indicated above. Special preference is given to hydrogen,unsubstituted or hydroxyl-substituted C₁-C₄alkyl or phenyl, especiallyhydrogen or unsubstituted or hydroxyl-substituted C₁-C₄alkyl, preferablyhydrogen. Examples of the radical of formula —NR₁₄R₁₅ that may bementioned include —NH₂, —NHCH₂CH₂OH, —N(CH₂CH₂OH)₂, —N(CH₃)CH₂CH₂OH, andthe pyrrolidine, piperidine, piperazine, morpholine or azepane ring andalso 4-methyl-piperazin-1-yl.

Preference is given to ligands of formula (2) wherein R₆ is nothydrogen.

R₆ is preferably C₁-C₁₂alkyl; phenyl unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl, sulfo,hydroxyl, amino, N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted orsubstituted by hydroxy in the alkyl moiety, N-phenylamino,N-naphthylamino, phenyl, phenoxy or by naphthoxy; cyano; halogen; nitro;—COOR₁₂ or —SO₃R₁₂ wherein R₁₂ is in each case hydrogen, a cation,C₁-C₁₂alkyl, or phenyl unsubstituted or substituted as indicated above;—SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in each case hydrogen,C₁-C₁₂alkyl, or phenyl unsubstituted or substituted as indicated above;—N(R₁₃)—NR′₁₃R″₁₃ wherein R₁₃, R′₁₃ and R″₁₃ are as defined above forR₁₃; —NR₁₄R₁₅ or —N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are eachindependently of the other(s) hydrogen, unsubstituted orhydroxyl-substituted C₁-C₁₂alkyl, or phenyl unsubstituted or substitutedas indicated above, or R₁₄ and R₁₅ together with the nitrogen atombonding them form an unsubstituted or C₁-C₄alkyl-substitutedpyrrolidine, piperidine, piperazine, morpholine or azepane ring.

R₆ is especially phenyl unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, phenyl or by hydroxyl; cyano; nitro; —COOR₁₂ or—SO₃R₁₂ wherein R₁₂ is in each case hydrogen, a cation, C₁-C₄alkyl orphenyl; —SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in each case hydrogen,C₁-C₄alkyl or phenyl; —N(CH₃)—NH₂ or —NH—NH₂; amino; N-mono- orN,N-di-C₁-C₄-alkylamino unsubstituted or substituted by hydroxy in thealkyl moiety; or an unsubstituted or C₁-C₄alkyl-substituted pyrrolidine,piperidine, piperazine, morpholine or azepane ring.

R₆ is very especially C₁-C₄alkoxy; hydroxy; phenyl unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, phenyl or by hydroxy; hydrazino;amino; N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or substituted byhydroxy in the alkyl moiety; or an unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring.

Especially important as radicals R₆ are C₁-C₄alkoxy; hydroxy; hydrazino;amino; N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or substituted byhydroxy in the alkyl moiety; or the unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring.

Very especially important as radicals R₆ are C₁-C₄alkoxy; hydroxy;N-mono- or N,N-di-C₁-C₄alkylamino substituted by hydroxy in the alkylmoiety; or the unsubstituted or C₁-C₄alkyl-substituted pyrrolidine,piperidine, piperazine, morpholine or azepane ring, hydroxyl being ofparticular interest.

The preferred meanings indicated above for R₆ apply also to R₁, R₂, R₃,R₄, R₅, R₇, R₈, R₉, R₁₀ and R₁₁, but those radicals may additionallydenote hydrogen.

In accordance with one embodiment of the present invention, R₁, R₂, R₃,R₄, R₅, R₇, R₈, R₉, R₁₀ and R₁₁ are hydrogen and R₆ is a radical otherthan hydrogen having the definitions and preferred meanings indicatedabove.

In accordance with a further embodiment of the present invention, R₁,R₂, R₄, R₅, R₇, R₈, R₁₀ and R₁₁ are hydrogen and R₃, R₆ and R₉ areradicals other than hydrogen having the definitions and preferredmeanings indicated above for R₆.

Preferred ligands L are those of formula

wherein R′₃ and R′₉ have the definitions and preferred meaningsindicated above for R₃ and R₉, and R′₆ has the definitions and preferredmeanings indicated above for R₆.

R′₃, R′₆ and R′₉ are preferably each independently of the othersC₁-C₄alkoxy; hydroxy; phenyl unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, phenyl or by hydroxy; hydrazino; amino; N-mono- orN,N-di-C₁-C₄alkylamino unsubstituted or substituted by hydroxy in thealkyl moiety; or an unsubstituted or C₁-C₄alkyl-substituted pyrrolidine,piperidine, piperazine, morpholine or azepane ring.

The metal complex compounds of formula (1) are known or can be obtainedanalogously to known processes. They are obtained in a manner known perse by reacting at least one ligand of formula (2) in the desired molarratio with a metal compound, especially a metal salt, such as thechloride, to form the corresponding metal complex. The reaction iscarried out, for example, in a solvent, such as water or a loweralcohol, such as ethanol, at a temperature of e.g. from 10 to 60° C.,especially at room temperature.

Ligands of formula (2) that are substituted by hydroxyl can also beformulated as compounds having a pyridone structure in accordance withthe following scheme (illustrated here using the example of aterpyridine substituted by hydroxyl in the 4′-position):

Their special place within the terpyridine family results from the factthat such ligands are capable of being deprotonated and are thereforeable to act as anionic ligands.

Generally, therefore, hydroxyl-substituted terpyridines are also to beunderstood as including those having a corresponding pyridone structure.

The ligands of formula (2) are known or can be prepared in a mannerknown per se. For that purpose, for example, two parts ofpyridine-2-carboxylic acid ester and one part of acetone can be reactedwith sodium hydride and the intermediate, a 1,3,5-triketone, obtainedafter aqueous working-up can be reacted with ammonium acetate tosynthesise the central pyridine ring. The corresponding pyridonederivatives are obtained, which can be converted into the chlorinecompounds by reaction with a chlorinating agent, such as PCl₅/POCl₃.Reactions of such compounds with amines, if desired in the presence ofan excess of redox-active transition metal salts, such as iron orruthenium, in order to accelerate the substitution, yieldamine-substituted terpyridines. Such preparation processes aredescribed, for example, in J. Chem. Soc., Dalton Trans. 1990, 1405-1409(E. C. Constable et al.) and New. J. Chem. 1992, 16, 855-867.

It has now been found that for the accelerated substitution of halide byamine at the terpyridine structure it is also possible to use catalyticamounts of non-transition metal salts, such as zinc(II) salts, whichconsiderably simplifies the reaction procedure and working-up.

The present invention relates also to novel metal complex compounds offormula

[L_(n)Me_(m)X_(p)]^(z)Y_(q)  (1a),

wherein Me is manganese, titanium, iron, cobalt, nickel or copper,X is a coordinating or bridging radical,n and m are each independently of the other an integer having a value offrom 1 to 8,p is an integer having a value from 0 to 32,z is the charge of the metal complex,Y is a counter-ion,q=z/(charge Y), andL is a ligand of formula

whereinR₆ is unsubstituted or substituted C₁-C₁₈alkyl; cyano; halogen; nitro;—COOR₁₂ or —SO₃R₁₂ wherein R₁₂ is in each case hydrogen, a cation orunsubstituted or substituted C₁-C₁₈alkyl or aryl; —SR₁₃, —SO₂R₁₃ or—OR₁₃ wherein R₁₃ is in each case hydrogen or unsubstituted orsubstituted C₁-C₁₈alkyl or aryl; —N(R₁₃)—NR′₁₃R″₁₃ wherein R₁₃, R′₁₃ andR″₁₃ are as defined above for R₁₃; —NR₁₄R₁₅ or —N^(⊕)R₁₄R₁₅R₁₆ whereinR₁₄, R₁₅ and R₁₆ are each independently of the other(s) hydrogen orunsubstituted or substituted C₁-C₁₈alkyl or aryl, or R₁₄ and R₁₅together with the nitrogen atom bonding them form an unsubstituted orsubstituted 5-, 6- or 7-membered ring which may optionally containfurther hetero atoms; andR₁, R₂, R₃, R₄, R₅, R₇, R₈, R₉, R₁₀ and R₁₁ are each independently ofthe others as defined above for R₆ or are hydrogen or unsubstituted orsubstituted aryl,with the proviso that when Me is titanium, iron, cobalt, nickel orcopper,R₃ and R₉ are not hydrogen and the three radicals R₃, R₆ and R₉ do nothave identical meanings.

The definitions and preferred meanings given above for the compounds offormula (1) apply also to the metal complex compounds of formula (1a).

The ligand L of the metal complex compounds of formula (1a) isespecially a compound of formula

whereinR′₆ is C₁-C₁₂alkyl; cyano; halogen; nitro; —COOR₁₂ or —SO₃R₁₂ whereinR₁₂ is in each case hydrogen, a cation, C₁-C₁₂alkyl, or phenylunsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano,nitro, carboxyl, sulfo, hydroxyl, amino, N-mono- orN,N-di-C₁-C₄alkylamino unsubstituted or substituted by hydroxy in thealkyl moiety, N-phenylamino, N-naphthylamino, phenyl, phenoxy or bynaphthoxy; —SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in each case hydrogen,C₁-C₁₂alkyl, or phenyl unsubstituted or substituted as indicated above;—N(R₁₃)—NR′₁₃R″₁₃ wherein R₁₃, R′₁₃ and R″₁₃ are as defined above forR₁₃; —NR₁₄R₁₅ or —N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are eachindependently of the other(s) hydrogen, unsubstituted orhydroxyl-substituted C₁-C₁₂alkyl, or phenyl unsubstituted or substitutedas indicated above, or R₁₄ and R₁₅ together with the nitrogen atombonding them form an unsubstituted or C₁-C₄alkyl-substitutedpyrrolidine, piperidine, piperazine, morpholino or azepane ring; andR′₃ and R′₉ are as defined above or are hydrogen or phenyl unsubstitutedor substituted as indicated above. The definitions and preferredmeanings indicated above for R′₆ and R′₃ and R′₉ likewise apply here.

The present invention relates also to the novel ligands of formula

whereinR₆ is cyano; halogen; nitro; —COOR₁₂ or —SO₃R₁₂ wherein R₁₂ is in eachcase hydrogen, a cation or unsubstituted or substituted C₁-C₁₈alkyl oraryl; —SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in each case hydrogen orunsubstituted or substituted C₁-C₁₈alkyl or aryl; —N(R₁₃)—NR′₁₃R″₁₃wherein R₁₃, R′₁₃ and R″₁₃ are as defined above for R₁₃; —NR₁₄R₁₅ or—N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are each independently of theother(s) hydrogen or unsubstituted or substituted C₁-C₁₈alkyl or aryl,or R₁₄ and R₁₅ together with the nitrogen atom bonding them form anunsubstituted or substituted 5-, 6- or 7-membered ring which mayoptionally contain further hetero atoms; andR₁, R₂, R₃, R₄, R₅, R₇, R₈, R₉, R₁₀ and R₁₁ are each independently ofthe others as defined above for R₆ or are hydrogen or unsubstituted orsubstituted C₁-C₁₈alkyl or aryl,with the proviso that the three radicals R₃, R₆ and R₉ do not haveidentical meanings.

The definitions and preferred meanings indicated above for the ligandsof formula (2) also apply here.

Preference is given to ligands of formula

whereinR₁₆ is cyano; halogen; nitro; —COOR₁₂ or —SO₃R₁₂ wherein R₁₂ is in eachcase hydrogen, a cation, C₁-C₁₂alkyl, or phenyl unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl,sulfo, hydroxyl, amino, N-mono- or N,N-di-C₁-C₄alkylamino unsubstitutedor substituted by hydroxy in the alkyl moiety, N-phenylamino,N-naphthylamino, phenyl, phenoxy or by naphthoxy; —SR₁₃, —SO₂R₁₃ or—OR₁₃ wherein R₁₃ is in each case hydrogen, C₁-C₁₂alkyl, or phenylunsubstituted or substituted as indicated above; —N(R₁₃)—NR′₁₃R″₁₃wherein R₁₃, R′₁₃ and R″₁₃ are as defined above for R₁₃; —NR₁₄R₁₅ or—N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are each independently of theother(s) hydrogen, unsubstituted or hydroxyl-substituted C₁-C₁₂alkyl, orphenyl unsubstituted or substituted as indicated above, or R₁₄ and R₁₅together with the nitrogen atom bonding them form an unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring; andR′₃ and R′₉ are as defined above or are hydrogen, C₁-C₁₂alkyl, or phenylunsubstituted or substituted as indicated above. The definitions andpreferred meanings indicated above for R′₆ and R′₃ and R′₉ for theligands of the metal complex compounds of formula (1) likewise applyhere.

The metal complex compounds of formula (1) are preferably used togetherwith peroxy compounds. Examples that may be mentioned in that regardinclude the following uses:

a) the bleaching of spots or stains on textile material in the contextof a washing process;b) the prevention of redeposition of migrating dyes during the washingof textile material;c) the cleaning of hard surfaces, especially table- and kitchen-ware orglass;d) the cleaning of hard surfaces, especially wall tiles or floor tiles,more especially for removing mold stains;e) use in washing and cleaning solutions having an antibacterial action;f) as pretreatment agents for bleaching textiles;g) as catalysts in selective oxidation reactions in the context oforganic synthesis.

A further use relates to the use of the metal complex compounds offormula (1) as catalysts for reactions with peroxy compounds forbleaching in the context of paper-making. This relates especially to thebleaching of pulp, which can be carried out in accordance with customaryprocesses. Also of interest is the use of the metal complex compounds offormula (1) as catalysts for reactions with peroxy compounds for thebleaching of waste printed paper.

Preference is given to the bleaching of spots or stains on textilematerial, the prevention of the redeposition of migrating dyes in thecontext of a washing process, or the cleaning of hard surfaces,especially table- or kitchen-ware or glass. For those purposes it ispreferable to use aqueous formulations of the metal complex compounds offormula (1).

It should be emphasised that the metal complex compounds do not causeany appreciable damage to fibres and dyeings, for example in thebleaching of textile material.

Processes for preventing the redeposition of migrating dyes in a washingliquor are usually carried out by adding to the washing liquor, whichcontains a peroxide-containing washing agent, one or more metal complexcompounds of formula (1) in an amount of from 0.1 to 200 mg, preferablyfrom 1 to 75 mg, especially from 3 to 50 mg, per litre of washingliquor. It will be understood that in such an application, as well as inthe other applications, the metal complex compounds of formula (1) canalternatively be formed in situ, the metal salt (e.g. manganese(II)salt, such as manganese(II) chloride) and the ligand being added in thedesired molar ratios.

The present invention relates also to a washing, cleaning, disinfectingor bleaching agent, containing

-   I) 0-50%, preferably 0-30%, A) of an anionic surfactant and/or B) of    a non-ionic surfactant,-   II) 0-70%, preferably 0-50%, C) of a builder substance,-   III) 1-99%, preferably 1-50%, D) of a peroxide or a peroxide-forming    substance, and-   IV) E) a metal complex compound of formula (1) in an amount which,    in the liquor, gives a concentration of 0.5-50 mg/litre of liquor,    preferably 1-30 mg/litre of liquor, when from 0.5 to 20 g/litre of    the washing, cleaning, disinfecting and bleaching agent are added to    the liquor.

The above percentages are in each case percentages by weight, based onthe total weight of the agent. The agents preferably contain from 0.005to 2% of a metal complex compound of formula (1), especially from 0.01to 1% and preferably from 0.05 to 1%.

When the agents according to the invention comprise a component A)and/or B), the amount thereof is preferably 1-50%, especially 1-30%.

When the agents according to the invention comprise a component C), theamount thereof is preferably 1-70%, especially 1-50%. Special preferenceis given to an amount of from 5 to 50% and especially an amount of from10 to 50%.

Corresponding washing, cleaning, disinfecting or bleaching processes areusually carried out by using an aqueous liquor comprising a peroxide andfrom 0.1 to 200 mg of one or more compounds of formula (1) per litre ofliquor. The liquor preferably contains from 1 to 30 mg of the compoundof formula (1) per litre of liquor.

The agents according to the invention can be, for example, aperoxide-containing complete washing agent or a separate bleachingadditive. A bleaching additive is used for removing coloured stains ontextiles in a separate liquor before the clothes are washed with ableach-free washing agent. A bleaching additive can also be used in aliquor together with a bleach-free washing agent.

The washing or cleaning agent according to the invention can be in solidor liquid form, for example in the form of a liquid, non-aqueous washingagent, comprising not more than 5% by weight water, preferablycomprising from 0 to 1% by weight water, and, as base, a suspension of abuilder substance in a non-ionic surfactant, e.g. as described in GB-A-2158 454.

The washing or cleaning agent is preferably in the form of a powder or,especially, granules.

The latter can be prepared, for example, by first preparing an initialpowder by spray-drying an aqueous suspension containing all thecomponents listed above except for components D) and E), and then addingthe dry components D) and E) and mixing everything together. It is alsopossible to add component E) to an aqueous suspension containingcomponents A), B) and C), then to carry out spray-drying and then to mixcomponent D) with the dry mass.

It is also possible to start with an aqueous suspension that containscomponents A) and C), but none or only some of component B). Thesuspension is spray-dried, then component E) is mixed with component B)and added, and then component D) is mixed in in the dry state.

It is also possible to mix all the components together in the dry state.

The anionic surfactant A) can be, for example, a sulfate, sulfonate orcarboxylate surfactant or a mixture thereof. Preferred sulfates arethose having from 12 to 22 carbon atoms in the alkyl radical, optionallyin combination with alkyl ethoxysulfates in which the alkyl radical hasfrom 10 to 20 carbon atoms.

Preferred sulfonates are e.g. alkylbenzenesulfonates having from 9 to 15carbon atoms in the alkyl radical. The cation in the case of anionicsurfactants is preferably an alkali metal cation, especially sodium.

Preferred carboxylates are alkali metal sarcosinates of formulaR—CO—N(R′¹)—CH₂COOM′¹ wherein R is alkyl or alkenyl having from 8 to 18carbon atoms in the alkyl or alkenyl radical, R′¹ is C₁-C₄alkyl and M′¹is an alkali metal.

The non-ionic surfactant B) can be, for example, a condensation productof from 3 to 8 mol of ethylene oxide with 1 mol of a primary alcoholhaving from 9 to 15 carbon atoms.

As builder substance C) there come into consideration, for example,alkali metal phosphates, especially tripolyphosphates, carbonates orhydrogen carbonates, especially their sodium salts, silicates,aluminosilicates, polycarboxylates, polycarboxylic acids, organicphosphonates, aminoalkylenepoly(alkylenephosphonates) or mixtures ofthose compounds.

Especially suitable silicates are sodium salts of crystalline layeredsilicates of the formula NaHSi_(t)O_(2t+1).pH₂O orNa₂Si_(t)O_(2t+1).pH₂O wherein t is a number from 1.9 to 4 and p is anumber from 0 to 20.

Among the aluminosilicates, preference is given to those commerciallyavailable under the names zeolite A, B, X and HS, and also to mixturescomprising two or more of those components.

Among the polycarboxylates, preference is given topolyhydroxycarboxylates, especially citrates, and acrylates and alsocopolymers thereof with maleic anhydride. Preferred polycarboxylic acidsare nitrilotriacetic acid, ethylenediaminetetraacetic acid andethylenediamine disuccinate either in racemic form or in theenantiomerically pure (S,S) form.

Phosphonates or aminoalkylenepoly(alkylenephosphonates) that areespecially suitable are alkali metal salts of1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonicacid), ethylenediaminetetramethylenephosphonic acid anddiethylenetriaminepentamethylenephosphonic acid.

As the peroxide component D) there come into consideration, for example,the organic and inorganic peroxides known in the literature andavailable commercially that bleach textile materials at conventionalwashing temperatures, for example at from 10 to 95° C.

The organic peroxides are, for example, mono- or poly-peroxides,especially organic peracids or salts thereof, such asphthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanedioicacid, diperoxynonanedioic acid, diperoxydecanedioic acid,diperoxyphthalic acid or salts thereof.

Preferably, however, inorganic peroxides are used, for examplepersulfates, perborates, percarbonates and/or persilicates. It will beunderstood that mixtures of inorganic and/or organic peroxides can alsobe used. The peroxides may be in a variety of crystalline forms and havedifferent water contents, and they may also be used together with otherinorganic or organic compounds in order to improve their storagestability.

The peroxides are added to the agent preferably by mixing thecomponents, for example using a screw metering system and/or a fluidisedbed mixer.

The agents may comprise, in addition to the combination according to theinvention, one or more optical brighteners, for example from the classbis-triazinylamino-stilbenedisulfonic acid,bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl orbis-benzofuranylbiphenyl, a bis-benzoxalyl derivative,bis-benzimidazolyl derivative or coumarin derivative or a pyrazolinederivative.

The agent may also comprise suspending agents for dirt, e.g. sodiumcarboxymethylcellulose, pH regulators, e.g. alkali metal or alkalineearth metal silicates, foam regulators, e.g. soap, salts for regulatingthe spray-drying and the granulating properties, e.g. sodium sulfate,perfumes and, optionally, antistatic agents and softeners, enzymes, suchas amylase, bleaches, pigments and/or toning agents. Such constituentsmust especially be stable towards the bleaching agent used.

In addition to the bleach catalyst according to formula (1) it is alsopossible to use further transition metal salts or complexes known asbleach-activating active ingredients and/or conventional bleachactivators, that is to say compounds that, under perhydrolysisconditions, yield unsubstituted or substituted perbenzo- and/orperoxo-carboxylic acids having from 1 to 10 carbon atoms, especiallyfrom 2 to 4 carbon atoms. Suitable bleach activators include thecustomary bleach activators, mentioned at the beginning, that carry O-and/or N-acyl groups having the indicated number of carbon atoms and/orunsubstituted or substituted benzoyl groups. Preference is given topolyacylated alkylenediamines, especially tetraacetylethylenediamine(TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU),N,N-diacetyl-N,N-dimethylurea (DDU), acylated triazine derivatives,especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),compounds of formula (4):

wherein R′₁ is a sulfonate group, a carboxylic acid group or acarboxylate group, and wherein R′₂ is linear or branched (C₇-C₁₅)alkyl,especially activators known under the names SNOBS, SLOBS and DOBA,acylated polyhydric alcohols, especially triacetin, ethylene glycoldiacetate and 2,5-diacetoxy-2,5-dihydrofuran, and also acetylatedsorbitol and mannitol and acylated sugar derivatives, especiallypentaacetylglucose (PAG), sucrose polyacetate (SUPA),pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well asacetylated, optionally N-alkylated glucamine and gluconolactone. It isalso possible to use the combinations of conventional bleach activatorsknown from German Patent Application DE-A-44 43 177. Nitrile compoundsthat form perimine acids with peroxides also come into consideration asbleach activators.

Further preferred additives to the agents according to the invention arepolymers which, during the washing of textiles, prevent staining causedby dyes in the washing liquor that have been released from the textilesunder the washing conditions. Such polymers are preferablypolyvinylpyrrolidones or polyvinylpyridine-N-oxides which may have beenmodified by the incorporation of anionic or cationic substituents,especially those having a molecular weight in the range of from 5000 to60 000, more especially from 10 000 to 50 000. Such polymers arepreferably used in an amount of from 0.05 to 5% by weight, especiallyfrom 0.2 to 1.7% by weight, based on the total weight of the washingagent.

The invention relates also to granules that comprise the catalystsaccording to the invention and are suitable for incorporation into apowder- or granule-form washing, dishwashing, cleaning or bleachingagent. Such granules preferably comprise:

-   a) from 1 to 99% by weight, preferably from 1 to 40% by weight,    especially from 1 to 30% by weight, of a metal complex compound of    formula (1), especially of formula (Ia),-   b) from 1 to 99% by weight, preferably from 10 to 99% by weight,    especially from 20 to 80% by weight, of a binder,-   c) from 0 to 20% by weight, especially from 1 to 20% by weight, of    an encapsulating material,-   d) from 0 to 20% by weight of a further additive and-   e) from 0 to 20% by weight of water.

As binder (b) there come into consideration anionic dispersants,non-ionic dispersants, polymers and waxes that are water-soluble,dispersible or emulsifiable in water.

The anionic dispersants used are, for example, commercially availablewater-soluble anionic dispersants for dyes, pigments etc.

The following products, especially, come into consideration:condensation products of aromatic sulfonic acids and formaldehyde,condensation products of aromatic sulfonic acids with unsubstituted orchlorinated diphenylene or diphenyl oxides and optionally formaldehyde,(mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerisedorganic sulfonic acids, sodium salts of polymerisedalkylnaphthalenesulfonic acids, sodium salts of polymerisedalkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkylpolyglycol ether sulfates, polyalkylated polynuclear arylsulfonates,methylene-linked condensation products of arylsulfonic acids andhydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acids,sodium salts of alkyl diglycol ether sulfates, sodium salts ofpolynaphthalenemethanesulfonates, lignosulfonates or oxylignosulfonatesor heterocyclic polysulfonic acids.

Especially suitable anionic dispersants are condensation products ofnaphthalenesulfonic acids with formaldehyde, sodium salts of polymerisedorganic sulfonic acids, (mono-/di-)alkylnaphthalenesulfonates,polyalkylated polynuclear arylsulfonates, sodium salts of polymerisedalkylbenzenesulfonic acids, lignosulfonates, oxylignosulfonates andcondensation products of naphthalenesulfonic acid with apolychloromethyldiphenyl.

Suitable non-ionic dispersants are especially compounds having a meltingpoint of, preferably, at least 35° C. that are emulsifiable, dispersibleor soluble in water, for example the following compounds:

-   1. fatty alcohols having from 8 to 22 carbon atoms, especially cetyl    alcohol;-   2. addition products of, preferably, from 2 to 80 mol of alkylene    oxide, especially ethylene oxide, wherein some of the ethylene oxide    units may have been replaced by substituted epoxides, such as    styrene oxide and/or propylene oxide, with higher unsaturated or    saturated monoalcohols, fatty acids, fatty amines or fatty amides    having from 8 to 22 carbon atoms or with benzyl alcohols, phenyl    phenols, benzyl phenols or alkyl phenols, the alkyl radicals of    which have at least 4 carbon atoms;-   3. alkylene oxide, especially propylene oxide, condensation products    (block polymers);-   4. ethylene oxide/propylene oxide adducts with diamines, especially    ethylenediamine;-   5. reaction products of a fatty acid having from 8 to 22 carbon    atoms and a primary or secondary amine having at least one    hydroxy-lower alkyl or lower alkoxy-lower alkyl group, or alkylene    oxide addition products of such hydroxyalkyl-group-containing    reaction products;-   6. sorbitan esters, preferably with long-chain ester groups, or    ethoxylated sorbitan esters, such as polyoxyethylene sorbitan    monolaurate having from 4 to 10 ethylene oxide units or    polyoxyethylene sorbitan trioleate having from 4 to 20 ethylene    oxide units;-   7. addition products of propylene oxide with a tri- to hexa-hydric    aliphatic alcohol having from 3 to 6 carbon atoms, e.g. glycerol or    pentaerythritol; and-   8. fatty alcohol polyglycol mixed ethers, especially addition    products of from 3 to 30 mol of ethylene oxide and from 3 to 30 mol    of propylene oxide with aliphatic monoalcohols having from 8 to 22    carbon atoms.

Especially suitable non-ionic dispersants are surfactants of formula

R′₁₁—O-(alkylene-O)_(n)—R′₁₂  (5),

wherein

-   R′₁₁ is C₈-C₂₂alkyl or C₈-C₁₈alkenyl;-   R′₁₂ is hydrogen; C₁-C₄alkyl; a cycloaliphatic radical having at    least 6 carbon atoms; or benzyl;-   “alkylene” is an alkylene radical having from 2 to 4 carbon atoms    and-   n is a number from 1 to 60.

A substituent R′₁₁ or R′₁₂ in formula (5) is advantageously thehydrocarbon radical of an unsaturated or, preferably, saturatedaliphatic monoalcohol having from 8 to 22 carbon atoms. The hydrocarbonradical may be straight-chain or branched. R′₁₁ and R′₁₂ are preferablyeach independently of the other an alkyl radical having from 9 to 14carbon atoms.

Aliphatic saturated monoalcohols that come into consideration includenatural alcohols, e.g. lauryl alcohol, myristyl alcohol, cetyl alcoholor stearyl alcohol, and also synthetic alcohols, e.g. 2-ethylhexanol,1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol,trimethylhexanol, trimethylnonyl alcohol, decanol, C₉-C₁₁oxo-alcohol,tridecyl alcohol, isotridecyl alcohol and linear primary alcohols(Alfols) having from 8 to 22 carbon atoms. Some examples of such Alfolsare Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) and Alfol(16-18). (“Alfol” is a registered trade mark).

Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol,hexadecenyl alcohol and oleyl alcohol.

The alcohol radicals may be present singly or in the form of mixtures oftwo or more components, e.g. mixtures of alkyl and/or alkenyl groupsthat are derived from soybean fatty acids, palm kernel fatty acids ortallow oils.

(Alkylene-O) chains are preferably divalent radicals of the formulae

Examples of a cycloaliphatic radical are cycloheptyl, cyclooctyl andpreferably cyclohexyl.

As non-ionic dispersants there come into consideration especiallysurfactants of formula

whereinR₁₃ is C₈-C₂₂alkyl;R₁₄ is hydrogen or C₁-C₄alkyl;Y₁, Y₂, Y₃ and Y₄ are each independently of the others hydrogen, methylor ethyl;n₂ is a number from 0 to 8; andn₃ is a number from 2 to 40.

Further important non-ionic dispersants correspond to formula

whereinR₁₅ is C₉-C₁₄alkyl;R₁₆ is C₁-C₄alkyl;Y₅, Y₆, Y₇ and Y₈ are each independently of the others hydrogen, methylor ethyl, one of the radicals Y₅, Y₆ and one of the radicals Y₇, Y₈always being hydrogen; andn₄ and n₅ are each independently of the other an integer from 4 to 8.

The non-ionic dispersants of formulae (5) to (7) can be used in the formof mixtures. For example, as surfactant mixtures there come intoconsideration non-end-group-terminated fatty alcohol ethoxylates offormula (5), e.g. compounds of formula (5) wherein

R₁₁ is C₈-C₂₂alkyl,R₁₂ is hydrogen andthe alkylene-O chain is the radical —(CH₂—CH₂—O)—and also end-group-terminated fatty alcohol ethoxylates of formula (7).

Examples of non-ionic dispersants of formulae (5), (6) and (7) includereaction products of a C₁₀-C₁₃fatty alcohol, e.g. a C₁₃oxo-alcohol, withfrom 3 to 10 mol of ethylene oxide, propylene oxide and/or butyleneoxide or the reaction product of one mol of a C₁₃fatty alcohol with 6mol of ethylene oxide and 1 mol of butylene oxide, it being possible forthe addition products each to be end-group-terminated with C₁-C₄alkyl,preferably methyl or butyl.

Such dispersants can be used singly or in the form of mixtures of two ormore dispersants.

Instead of, or in addition to, the anionic or non-ionic dispersant, thegranules according to the invention may comprise a water-soluble organicpolymer as binder. Such polymers may be used singly or in the form ofmixtures of two or more polymers.

Water-soluble polymers that come into consideration are, for example,polyethylene glycols, copolymers of ethylene oxide with propylene oxide,gelatin, polyacrylates, polymethacrylates, polyvinylpyrrolidones,vinylpyrrolidones, vinyl acetates, polyvinylimidazoles,polyvinylpyridine-N-oxides, copolymers of vinylpyrrolidone withlong-chain α-olefins, copolymers of vinylpyrrolidone withvinylimidazole, poly(vinylpyrrolidone/dimethylaminoethyl methacrylates),copolymers of vinylpyrrolidone/dimethylaminopropyl methacrylamides,copolymers of vinylpyrrolidone/dimethylaminopropyl acrylamides,quaternised copolymers of vinylpyrrolidones and dimethylaminoethylmethacrylates, terpolymers ofvinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates,copolymers of vinylpyrrolidone andmethacrylamidopropyl-trimethylammonium chloride, terpolymers ofcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates,copolymers of styrene and acrylic acid, polycarboxylic acids,polyacrylamides, carboxymethylcellulose, hydroxymethylcellulose,polyvinyl alcohols, polyvinyl acetate, hydrolysed polyvinyl acetate,copolymers of ethyl acrylate with methacrylate and methacrylic acid,copolymers of maleic acid with unsaturated hydrocarbons, and also mixedpolymerisation products of the mentioned polymers.

Of those organic polymers, special preference is given to polyethyleneglycols, carboxymethylcellulose, polyacrylamides, polyvinyl alcohols,polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, and alsopolyacrylates, copolymers of ethyl acrylate with methacrylate andmethacrylic acid, and polymethacrylates.

Suitable water-emulsifiable or water-dispersible binders also includeparaffin waxes.

Encapsulating materials (c) include especially water-soluble andwater-dispersible polymers and waxes. Of those materials, preference isgiven to polyethylene glycols, polyamides, polyacrylamides, polyvinylalcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, and alsopolyacrylates, paraffins, fatty acids, copolymers of ethyl acrylate withmethacrylate and methacrylic acid, and polymethacrylates.

Further additives (d) that come into consideration are, for example,wetting agents, dust removers, water-insoluble or water-soluble dyes orpigments, and also dissolution accelerators, optical brighteners andsequestering agents.

The preparation of the granules according to the invention is carriedout, for example, starting from:

a) a solution or suspension with a subsequent drying/shaping step orb) a suspension of the active ingredient in a melt with subsequentshaping and solidification.

a) First of all the anionic or non-ionic dispersant and/or the polymerand, if appropriate, the further additives are dissolved in water andstirred, if desired with heating, until a homogeneous solution has beenobtained. The catalyst according to the invention is then dissolved orsuspended in the resulting aqueous solution. The solids content of thesolution should preferably be at least 30% by weight, especially 40 to50% by weight, based on the total weight of the solution. The viscosityof the solution is preferably less than 200 mPas.

The aqueous solution so prepared, comprising the catalyst according tothe invention, is then subjected to a drying step in which all water,with the exception of a residual amount, is removed, solid particles(granules) being formed at the same time. Known methods are suitable forproducing the granules from the aqueous solution. In principle, bothcontinuous methods and discontinuous methods are suitable. Continuousmethods are preferred, especially spray-drying and fluidised bedgranulation processes.

Especially suitable are spray-drying processes in which the activeingredient solution is sprayed into a chamber with circulating hot air.The atomisation of the solution is effected e.g. using unitary or binarynozzles or is brought about by the spinning effect of a rapidly rotatingdisc. In order to increase the particle size, the spray-drying processmay be combined with an additional agglomeration of the liquid particleswith solid nuclei in a fluidised bed that forms an integral part of thechamber (so-called fluid spray). The fine particles (<100 μm) obtainedby a conventional spray-drying process may, if necessary after beingseparated from the exhaust gas flow, be fed as nuclei, without furthertreatment, directly into the atomizing cone of the atomiser of thespray-dryer for the purpose of agglomeration with the liquid droplets ofthe active ingredient.

During the granulation step, the water can rapidly be removed from thesolutions comprising the catalyst according to the invention, binder andfurther additives. It is expressly intended that agglomeration of thedroplets forming in the atomising cone, or the agglomeration of dropletswith solid particles, will take place.

If necessary, the granules formed in the spray-dryer are removed in acontinuous process, for example by a sieving operation. The fines andthe oversize particles are either recycled directly to the process(without being redissolved) or are dissolved in the liquid activeingredient formulation and subsequently granulated again.

A further preparation method according to a) is a process in which thepolymer is mixed with water and then the catalyst is dissolved/suspendedin the polymer solution, thus forming an aqueous phase, the catalystaccording to the invention being homogeneously distributed in thatphase. At the same time or subsequently, the aqueous phase is dispersedin a waterimmiscible liquid in the presence of a dispersion stabiliserin order that a stable dispersion is formed. The water is then removedfrom the dispersion by distillation, forming substantially dryparticles. In those particles, the catalyst is homogeneously distributedin the polymer matrix.

The granules according to the invention are wear-resistant, low in dust,pourable and readily meterable. They can be added directly to aformulation, such as a washing agent formulation, in the desiredconcentration of the catalyst according to the invention.

Where the coloured appearance of the granules in the washing agent is tobe suppressed, this can be achieved, for example, by embedding thegranules in a droplet of a whitish meltable substance (“water-solublewax”) or by adding a white pigment (e.g. TiO₂) to the granuleformulation or, preferably, by encapsulating the granules in a meltconsisting, for example, of a water-soluble wax, as described in EP-A-0323 407, a white solid being added to the melt in order to reinforce themasking effect of the capsule.

b) The catalyst according to the invention is dried in a separate stepprior to the melt-granulation and, if necessary, dry-ground in a mill sothat all the solids particles are <50 μm in size. The drying is carriedout in an apparatus customary for the purpose, for example in a paddledryer, vacuum cabinet or freeze-dryer.

The finely particulate catalyst is suspended in the molten carriermaterial and homogenised. The desired granules are produced from thesuspension in a shaping step with simultaneous solidification of themelt. The choice of a suitable melt-granulation process is made inaccordance with the desired size of granules. In principle, any processwhich can be used to produce granules in a particle size of from 0.1 to4 mm is suitable. Such processes are droplet processes (withsolidification on a cooling belt or during free fall in cold air),meltprilling (cooling medium gas/liquid), and flake formation with asubsequent comminution step, the granulation apparatus being operatedcontinuously or discontinuously.

Where the coloured appearance of the granules prepared from a melt is tobe suppressed in the washing agent, in addition to the catalyst it isalso possible to suspend in the melt white or coloured pigments which,after solidification, impart the desired coloured appearance to thegranules (e.g. titanium dioxide).

If desired, the granules can be covered or encapsulated in anencapsulating material. Methods suitable for such an encapsulationinclude the customary methods and also the encapsulation of the granulesby a melt consisting e.g. of a water-soluble wax, as described, forexample, in EP-A-0 323 407, coacervation, complex coacervation andsurface polymerisation.

Encapsulating materials (c) include e.g. water-soluble,water-dispersible or water-emulsifiable polymers and waxes.

Further additives (d) include e.g. wetting agents, dust-removers,water-insoluble or water-soluble dyes or pigments, and also dissolutionaccelerators, optical brighteners and sequestering agents.

Surprisingly, the metal complex compounds of formula (1) also exhibit amarkedly improved bleach-catalysing action on coloured stains on hardsurfaces. The addition of such complexes in catalytic amounts to adishwashing agent that comprises a peroxy compound and optionally TAED(N,N,N′,N′-tetraacetylethylenediamine) results in the substantialremoval of e.g. tea stains on china. This is the case even when hardwater is used, it being known that tea deposits are more difficult toremove in hard water than in soft water. The compounds are also verysuitable for cleaning hard surfaces at low temperatures.

The use of metal complex compounds of formula (1) as catalysts forreactions with peroxy compounds in cleaning solutions for hard surfaces,especially for kitchen- and table-ware, is therefore of specialinterest.

The present invention relates also to cleaning agents for hard surfaces,especially cleaning agents for table- and kitchen-ware and, among suchagents, preferably those for use in cleaning processes carried out bymachine, which agents comprise one of the above-described metal complexcompounds of formula (1) as bleach catalyst. Suitable formulations forsuch cleaning agents include, for example, the formulations mentionedabove for the washing agents.

The metal complex compounds of formula (1) also have, together withperoxy compounds, excellent antibacterial action. The use of the metalcomplex compounds of formula (1) for killing bacteria or for protectingagainst bacterial attack is therefore likewise of interest.

The metal complex compounds of formula (1) are also outstandinglysuitable for selective oxidation in the context of organic synthesis,especially the oxidation of organic molecules, e.g. of olefins to formepoxides. Such selective transformation reactions are requiredespecially in process chemistry. The invention accordingly relates alsoto the use of the metal complex compounds of formula (1) in selectiveoxidation reactions in the context of organic synthesis.

The following Examples serve to illustrate the invention but do notlimit the invention thereto. Parts and percentages relate to weight,unless otherwise indicated.

EXAMPLES Synthesis of 4′-Substituted Terpyridines and 4-PyridonesExample 1 1′H-[2,2′;6′,2″]Terpyridin-4′-one (Referred to as L1 Below)

a) Step 1:

In a nitrogen atmosphere, under reflux, a solution of 20.2 ml (22.7 g,150 mmol) of pyridine-2-carboxylic acid ethyl ester and 3.6 ml (50 mmol)of dry acetone in 100 ml of dry tetrahydrofuran is added in the courseof 4 hours to a suspension of 6 g (approximately 60% dispersion inparaffin oil, about 150 mmol) of sodium hydride in 100 ml of drytetrahydrofuran. The mixture is boiled at reflux for a further 2 hoursand then concentrated using a rotary evaporator. After the addition of200 ml of ice-water, the mixture is rendered neutral with 50% strengthacetic acid and the resulting yellow1,5-di-pyridin-2-yl-pentane-1,3,5-trione is filtered off. IR (cm⁻¹):2953 (s); 2923 (vs); 2854 (m); 1605 (m); 1560 (s); 1447 (w); 1433 (w);1374 (m); 1280 (w); 786 (w).

b) Step 2:

A mixture of 10 g (37 mmol) of 1,5-di-pyridin-2-yl-pentane-1,3,5-trioneand 20 g (260 mmol) of ammonium acetate is boiled under reflux in 250 mlof ethanol for 8 hours. The mixture so obtained is concentrated to abouthalf its volume. After filtration, 1′H-[2,2′;6′,2″]terpyridine-4′-one isobtained in the form of a white solid. ¹H-NMR (360 MHz, DMSO-d6):7.40-7.50 (qm, 2H); 7.87 (s, 2H); 7.92-8.0 (tm, 2H); 8.57 (d, 2H, 7.7Hz); 8.68 (d, 2H, J=4.5 Hz), 10.9 (s, 1H). MS (EI pos., 70 eV), m/z=249(100, [M⁺]); 221 (40).

(for preparation see also K. T. Potts, D. Konwar, J. Org. Chem. 2000,56, 4815-4816 and E. C. Constable, M. D. Ward, J. Chem. Soc. DaltonTrans. 1990, 1405-1409).

Example 2 4′-Chloro-[2,2′;6′,2″]terpyridine (Referred to as L2 Below)

A mixture of 3.99 g (16 mmol) of 1′H-[2,2′;6′,2″]terpyridin-4′-one (L1)and 8.0 g (38 mmol) of phosphorus pentachloride is boiled at reflux in200 ml of phosphorus oxychloride for sixteen hours. The mixture isallowed to cool and concentrated to dryness. 200 ml of ice-water arethen added cautiously to the residue, and the solution is then adjustedto pH 9 with aqueous potassium hydroxide solution. Extraction is carriedout three times using chloroform and the organic extracts are dried oversodium sulfate, filtered and concentrated. After recrystallisation fromethanol, 4′-chloro-[2,2′;6′,2″]terpyridine is obtained in the form ofwhite needles. ¹H-NMR (CDCl₃, 360 MHz): 7.20-7.29 (m, 2H); 7.70-7.79(tm, 2H); 8.37 (s, 2H); 8.47 (d, 2H, 7.6 Hz); 8.56-8.63 (dm, 2H).

(for preparation see also E. C. Constable, M. D. Ward, J. Chem. Soc.Dalton Trans. 1990, 1405-1409).

Example 3 4′-Ethoxy-[2,2′;6′,2″]terpyridine (Referred to as L3 Below)

In a nitrogen atmosphere, 900 mg (3.4 mmol) of4′-chloro-[2,2′;6′,2″]terpyridine are added to 15 ml of a 0.7M ethanolicsodium ethanolate solution. The mixture is heated at reflux for 20hours. The mixture is allowed to cool and 20 ml of water are added, and4′-ethoxy-[2,2′;6′,2″]terpyridine is filtered off in the form of a whitesolid. ¹H-NMR (360 MHz, DMSO-d6): 1.40 (t, 3H, 6.8 Hz); 4.28 (q, 2H, 6.8Hz); 7.42-7.53 (m, 2H); 7.93 (s, 2H); 7.95-8.02 (m, 2H); 8.58 (d, 2H,J=8.1 Hz); 8.69 (d, 2H, J=4 Hz).

(for preparation see also E. C. Constable, A. M. W. Cargill Thompson,New. J. Chem. 1992, 16, 855-867).

Example 4 [2,2′;6′,2″]Terpyridin-4′-yl-hydrazine (Referred to as L4Below)

4 ml (126 mmol) of hydrazine are added to 600 mg (2.2 mmol) of4′-chloro-[2,2′;6′,2″]-terpyridine in 12 ml of 2-butanol. The mixture isheated at reflux for 17 hours and cooled, and[2,2′;6′,2″]terpyridin-4′-yl-hydrazine is filtered off in the form of awhite solid.

¹H-NMR (360 MHz, DMSO-d6): 4.38 (s br, 2H); 7.38-7.45 (m, 2H); 7.84 (s,2H); 7.88-7.97 (m, 3H); 8.52-8.57 (m, 2H); 8.64-8.76 (m, 2H).

(for preparation see also G. Lowe et al., J. Med. Chem., 1999, 42,999-1006).

Example 5 2-(Methyl-[2,2′;6′,2″]terpyridin-4′-yl-amino)-ethanol(Referred to as L5 Below)

A solution in 20 ml of dichloromethane of 1.61 g (6 mmol) of4′-chloro-2,2′:6′,2″-terpyridine and 20 ml of N-methylaminoethanol areadded in succession to a solution of 1.35 g (6.8 mmol) of iron(II)chloride tetrahydrate in 100 ml of isopropanol. The mixture is thenboiled at reflux for 20 hours. The mixture is concentrated and asolution of 1.66 g of ammonium hexafluorophosphate in 10 ml of methanolis added. The resulting violet precipitate is washed four times using 50ml of diethyl ether each time and once with 50 ml of water. The residueis then stirred for 14 hours in a solution of 4 g of sodium hydroxide in300 ml of water/acetonitrile (1:1 v/v) in an oxygen atmosphere.Filtration is carried out over kieselguhr and the residue is washed with50 ml of water, 50 ml of acetonitrile and 100 ml of dichloromethane. Thefiltrates are concentrated. Extraction is carried out four times withdichloromethane and the combined organic extracts are dried over sodiumsulfate, filtered and concentrated. The residue is recrystallised fromacetone/petroleum ether and acetonitrile;2-(methyl-[2,2′;6′,2″]terpyridin-4′-yl-amino)-ethanol is obtained in theform of a white solid. MS (ESI pos., KF), m/z=345 (100, [M+K]⁺); 307(35, [M+H]⁺).

(for preparation see also G. Lowe et al., J. Med. Chem., 1999, 42,999-1006).

Example 6 4′-Pyrrolidin-1-yl-[2,2′;6′,2″]terpyridine (Referred to as L6Below)

28 mg (<5 mol %) of zinc(II) chloride and 4.4 g (61.5 mmol) ofpyrrolidine are added in succession to a mixture of 1.1 g (4.1 mmol) of4′-chloro-[2,2′;6′,2″]terpyridine in 15 ml of 2-methyl-2-butanol. Themixture is heated at reflux for 20 hours, cooled and filtered. Afterrecrystallisation from toluene, pure4′-pyrrolidin-1-yl-[2,2′;6′,2″]terpyridine is obtained in the form of awhite solid. MS (EI, 70 eV): m/z=303 (15); 302 (90, [M⁺]); 273 (100);233 (25). ¹H-NMR (360 MHz, CDCl₃): 1.9-2.0 (m, 4H); 3.39-3.49 (m, 4H);7.18 (dd, 2H, J=6.7, 5.2 Hz); 7.51 (s, 2H); 7.66-7.76 (tm, 2H); 8.51 (d,2H, J=7.7 Hz); 8.54-8.60 (m, 2H).

Example 72-[(2-Hydroxy-ethyl)-[2,2′;6′,2″]terpyridin-4′-yl-amino]-ethanol(Referred to as L7 Below)

3.41 g (17.2 mmol) of manganese(II) chloride tetrahydrate and 98 g (0.93mol) of diethanolamine are added in succession to a mixture of 2.14 g (8mmol) of 4′-chloro-[2,2′;6′,2″]-terpyridine in 200 ml of methanol. Themixture is heated at reflux for 14 hours, cooled and concentrated. Theresidue so obtained is stirred in 250 ml of sodium hydroxide solution inacetonitrile/water 1:1 (v/v, pH>12) for 20 hours in air. Acetonitrile isremoved using a rotary evaporator and the aqueous portion is extractedthree times with chloroform. The organic extract is filtered over sodiumsulfate and concentrated. Diethyl ether is added to the residue and themixture is stirred and filtered, yielding2-[(2-hydroxy-ethyl)-[2,2′;6′,2″]-terpyridin-4′-yl-amino]-ethanol in theform of a white solid. ¹H-NMR (360 MHz, CD₃OD): 3.76 (t, J=5.4 Hz, 4H);3.85 (t, J=5.4 Hz, 4H); 7.38-7.47 (tm, 2H); 7.69 (s, 2H); 7.94 (dt,J=8.1, 1.8 Hz, 2H); 8.53 (d, J=8.1 Hz, 2H); 8.58-8.65 (dm, 2H).

Example 8 4′-(4-Methyl-piperazin-1-yl)-[2,2′;6′,2″]terpyridine (Referredto as L8 Below)

This compound is prepared analogously to the procedure indicated abovefor the preparation of the ligand L7 in Example 7, but1-methylpiperazine is used as amine component.4′-(4-Methyl-piperazin-1-yl)-[2,2′;6′,2″]terpyridine, white solid.¹³C-NMR (90 MHz, CDCl₃): 157.1 (2 signals, quart.); 156.3 (quart.);149.1 (tert.); 137.0 (tert.); 123.8 (tert); 121.6 (tert); 105.7 (tert.);55.0 (sec.); 46.6 (sec.); 46.4 (prim.). MS (EI pos., 70 eV), m/z=331(100, [M⁺]), 261 (95); 233 (40); 70 (40); 50 (43).

Example 8b 1,1-Dimethyl-4-[2,2′;6′,2″]terpyridin-4′-yl-piperazin-1-iumiodide (Referred to as L8b Below)

211 mg (0.64 mmol) of ligand L8 are dissolved in 11 ml of acetonitrileand at room temperature an excess of methyl iodide (2.1 ml) is addeddropwise thereto. The mixture is then stirred for 3 hours at roomtemperature and concentrated, and 10 ml of dichloromethane are added tothe residue. The precipitate is filtered off and dried in vacuo,1,1-dimethyl-4-[2,2′;6′,2″]terpyridin-4′-yl-piperazin-1-ium iodide,beige solid. ¹H-NMR (360 MHz, CD₃OD): 3.34 (s, 6H), 3.62-3.80 (m, 4H);3.85-4.03 (m, 4H); 7.39-7.52 (m, 2H); 7.86-8.03 (m, 4H); 8.57 (d, J=7.7Hz, 2H); 8.63 (d, J=4.5 Hz, 2H).

Example 9 4′-Azepan-1-yl-[2,2′;6′,2″]terpyridine (Referred to as L9Below)

This compound is prepared analogously to the procedure indicated abovefor the preparation of the ligand L7 in Example 7, buthexamethyleneimine is used as amine component.4′-Azepan-1-yl-[2,2′;6′,2″]terpyridine, white solid. ¹³C-NMR (90 MHz,CDCl₃): 157.7 (quart.); 156.1 (quart.); 155.6 (quart); 149.2 (tert.);137.0 (tert.); 123.7 (tert.); 121.8 (tert); 103.7 (tert); 49.4 (sec);27.9 (sec); 27.4 (sec). MS (EI pos., 70 eV), m/z=330 (100, [M⁺]); 287(45); 273 (25); 233 (20).

Example 10 4′-Piperidin-1-yl-[2,2′;6′,2″]terpyridine (Referred to as L10Below)

This compound is prepared analogously to the procedure indicated abovefor the preparation of the ligand L7 in Example 7, but piperidine isused as amine component. 4′-Piperidin-1-yl-[2,2′;6′,2″]terpyridine,white solid. ¹³C-NMR (CDCl₃): 157.4 (quart.); 157.3 (quart.); 156.2(quart.); 149.2 (tert.); 137.1 (tert.); 123.8 (tert); 121.8 (tert.);105.7 (tert.); 48.1 (sec.); 25.9 (sec.); 24.9 (sec.). MS (EI pos., 70eV), m/z=316 (100, [M⁺]); 287 (35); 261 (25); 233 (70).

Example 11 4′-Morpholin-4-yl-[2,2′;6′,2″]terpyridine (Referred to as L11Below)

This compound is prepared analogously to the procedure indicated abovefor the preparation of the ligand L7 in Example 7, but morpholine isused as amine component. 4′-Morpholin-4-yl-[2,2′;6′,2″]terpyridine,white solid. ¹³C-NMR (CDCl₃): 157.6 (quart.); 157.0 (quart.); 156.5(quart.); 149.2 (tert.); 137.2 (tert.); 124.0 (tert.); 121.8 (tert.);105.7 (tert.); 67.0 (sec.); 47.0 (sec.). MS (EI pos., 70 eV), m/z=318(100, [M⁺]); 287 (35); 261 (45); 233 (85).

Example 12 4′-(4-tert-Butyl-phenyl)-[2,2′;6′,2″]terpyridine (Referred toas L12 Below)

4.06 g (25 mmol) of 4-tert-butyl benzaldehyde are dissolved in 150 ml ofethanol. Sodium hydroxide solution (5.13 g in 40 ml of water) is addedand then 10.54 g (87 mmol) of 2-acetylpyridine are added dropwise over aperiod of 10 minutes. The mixture is then stirred at room temperaturefor 18 hours. The pale pink precipitate so obtained is filtered withsuction and washed with 10 ml each of methanol and water. A secondfraction is obtained from the mother liquor by adding water. 2.54 g ofthe residue so obtained are then taken up in 160 ml of glacial aceticacid; 32 g (excess) of ammonium acetate are added and the mixture isheated at reflux for 3 hours. The mixture is cooled, neutralised withsodium carbonate solution and extracted twice with dichloromethane. Themixture is dried over sodium sulfate and filtered and the organicextract is concentrated. After recrystallisation from methanol,4′-(4-tert-butyl-phenyl)-[2,2′;6′,2″]terpyridine is obtained in the formof a white solid. ¹³C-NMR (90 MHz, CDCl₃): 156.8 (quart.); 156.3(quart.); 152.7 (quart.); 150.5 (quart.); 149.5 (tert.); 137.2 (tert.);135.9 (quart.); 127.4 (tert.); 126.3 (tert.); 124.1 (tert.); 121.8(tert.); 119.2 (tert.); 35.0 (quart.); 31.6 (prim.).

(for preparation see also E. C. Constable, P. Harveson, D. R. Smith, L.Whall, Polyhedron 1997, 16, 3615-3623).

Example 13 4′-(4-Isopropyl-phenyl)-[2,2′;6′,2″]terpyridine (Referred toas L13 Below)

This compound is prepared analogously to the procedure described abovefor the preparation of the ligand L12 in Example 12, but 4-isopropylbenzaldehyde is used as carbonyl component.4′-(4-Isopropyl-phenyl)-[2,2′;6′,2″]terpyridine, white solid. ¹³C-NMR(90 MHz, CDCl₃): 155.4 (quart.); 155.0 (quart.); 149.3 (quart.); 149.1(quart.); 148.2 (tert.); 135.9 (tert.); 135.0 (quart.); 126.4 (tert.);125.8 (tert.); 122.8 (tert.); 120.5 (tert.); 117.6 (tert.); 30.0(tert.); 23.0 (prim.).

Example 14 4′-p-Tolyl-[2,2′;6′,2″]terpyridine (Referred to as L14 Below)

This compound is prepared analogously to the procedure described abovefor the preparation of the ligand L12 in Example 12, but4-methylbenzaldehyde is used as carbonyl component.4′-p-Tolyl-[2,2′;6′,2″]terpyridine, white solid. ¹³C-NMR (90 MHz,CDCl₃): 155.8 (quart.); 155.3 (quart.); 149.6 (quart.); 148.5 (tert.);138.5 (quart.); 136.0 (tert.); 134.9 (quart.); 128.7 (tert.); 126.6(tert.); 123.2 (tert.); 120.8 (tert.); 118.0 (tert.); 20.7 (prim.).

Example 15 4′-Biphenyl-4-yl-[2,2′;6′,2″]terpyridine (Referred to as L15Below)

This compound is prepared analogously to the procedure described abovefor the preparation of the ligand L12 in Example 12, but 4-phenylbenzaldehyde is used as carbonyl component.4′-Biphenyl-4-yl-[2,2′;6′,2″]terpyridine, white solid. ¹³C-NMR (90 MHz,CDCl₃): 156.6 (quart.); 156.3 (quart.); 150.0 (quart.); 149.5 (tert.);142.2 (quart.); 140.8 (quart.); 137.6 (quart.); 136.9 (tert.); 129.3(tert.); 128.1 (tert.); 128.0 (tert.); 127.9 (tert.); 126.3 (tert.);124.2 (tert.); 121.8 (tert.); 119.1 (tert.).

Synthesis of Building Blocks for Polysubstituted Ligands of the PyridoneType Example 16 4-Chloro-pyridine-2-carboxylic acid methyl ester a) Step1:

36.9 g (0.3 mol) of pyridine-2-carboxylic acid are dissolved in 105 mlof thionyl chloride. After the addition of 3.1 g (30 mmol) of sodiumbromide, the mixture is heated cautiously to reflux temperature. Boilingis continued for 24 hours, the gases formed being removed via a washbottle filled with sodium hydroxide solution. When the reaction iscomplete, the mixture is allowed to cool and concentrated using a rotaryevaporator.

b) Step 2:

300 ml of methanol are cautiously added, with stirring, at 0° C. to thebrown residue obtained in Step 1. The mixture is heated to roomtemperature and stirred for a further 30 minutes to complete thereaction. The mixture is concentrated and 750 ml of 5% strength sodiumhydrogen carbonate solution are added thereto; extraction is carried outthree times using ethyl acetate. The organic extracts are dried oversodium sulfate, filtered and concentrated. The crude product so obtainedis distilled in a sickle flask (about 100-120° C., 0.1 mbar).4-Chloro-pyridine-2-carboxylic acid methyl ester is obtained in the formof a white solid. ¹H-NMR (360 MHz, CDCl₃): 4.01 (s, 3H); 7.44 (dd, 1H,J=5.4, 1.8 Hz); 8.12 (d, 1H, J=1.8 Hz); 8.4 (d, 1H, J=5.4 Hz).

(for preparation see also R. J. Sundberg, S. Jiang, Org. Prep. Proced.Int. 1997, 29, 117-122).

Example 17 4-Ethoxy-pyridine-2-carboxylic acid ethyl ester

This compound is obtained in a manner analogous to that described inExample 16, except that in Step 2 ethanol is used instead of methanoland the mixture is heated at reflux for 24 hours after the addition ofalcohol. The purification of the crude product is effected bydistillation (100-105° C., 0.08 mbar). 4-Ethoxy-pyridine-2-carboxylicacid ethyl ester is obtained in the form of a colourless oil. ¹H-NMR(360 MHz, CDCl₃): 1.44 (m, 6H); 4.15 (q, 2H, J=7.0 Hz); 4.47 (q, 2H,J=7.0 Hz); 6.94 (dd, 1H, J=5.1, 2.7 Hz); 7.65 (d, 2H, J=2.7 Hz); 8.54(d, 1H; J=5.7 Hz).

Example 18 4-Pyrrolidin-1-yl-pyridine-2-carboxylic acid ethyl ester a)Step 1:

This step is carried out in a manner analogous to that described in Step1 in Example 16.

b) Step 2:

This step is carried out as described in T. Sammakia, T. B. Hurley, J.Org. Chem. 2000, 65, 974-978: to the resulting crude acid chloride indichloromethane there is added dropwise at 0° C. a dichloromethanesolution of a threefold excess of pyrrolidine and catalytic amounts ofN,N-dimethylaminopyridine. The mixture is then stirred for a further onehour at room temperature, then heated at reflux for 5 hours andconcentrated using a rotary evaporator. The residue is then extractedfive times with diethyl ether. The ethereal extracts are concentrated.The residue is then taken up in 6M hydrochloric acid and boiled atreflux for 6 hours. On concentration using a rotary evaporator, pure4-pyrrolidin-1-yl-pyridine-2-carboxylic acid is precipitated. For thesynthesis of 4-pyrrolidin-1-yl-pyridine-2-carboxylic acid ethyl ester,the carboxylic acid is taken up in thionyl chloride and heated atboiling for 30 minutes. Concentration is carried out using a rotaryevaporator and the procedure is then as described in Example 16, Step 2,except that ethanol is used as alcohol.

Example 19 1,5-Bis(4-chloro-pyridin-2-yl)pentane-1,3,5-trione

This compound is prepared in a manner analogous to that described inExample 1, Step 1, for pyridine-2-carboxylic acid ethyl ester, butinstead 4-chloro-pyridine-2-carboxylic acid methyl ester from Example 16is used. The beige solid crude product is used for further syntheseswithout special purification steps.

IR (cm⁻¹): 1619 (m); 1564 (s); 1546 (s); 1440 (m); 1374 (s); 1156 (m);822 (w).

Example 20 1,5-Bis(4-ethoxy-pyridin-2-yl)pentane-1,3,5-trione

This compound is prepared in a manner analogous to that described inExample 1, Step 1, for pyridine-2-carboxylic acid ethyl ester, butinstead 4-ethoxy-pyridine-2-carboxylic acid ethyl ester from Example 17is used. The yellowish crude product is used for further syntheseswithout special purification steps. IR (cm⁻¹): 1557 (vs); 1469 (w); 1436(w); 1300 (m); 1207 (m); 1186 (m); 1035 (m); 818 (m).

Example 21 1,5-Bis(4-pyrrolidin-1-yl-pyridin-2-yl)-pentane-1,3,5-trione

This compound is prepared in a manner analogous to that described inExample 1, Step 1, for pyridine-2-carboxylic acid ethyl ester, butinstead 4-pyrrolidin-1-yl-pyridine-2-carboxylic acid ethyl ester fromExample 18 is used. The yellow-orange crude product is used for furthersyntheses without special purification steps. IR (cm⁻¹): 1548 (s); 1504(s); 1453 (s); 1381 (s); 1349 (m); 1276 (w); 1243 (M); 1207 (w); 796(w).

Synthesis of Polysubstituted Terpyridines and Pyridones Example 224,4″-Dichloro-1′H-[2,2′;6′,2″]terpyridin-4′-one (Referred to as L16Below)

This compound is prepared in a manner analogous to that described inExample 1, Step 2, for 1,5-di-pyridin-2-yl-pentane-1,3,5-trione, butinstead the chloro-substituted triketone from Example 19 is used. Pure4,4″-dichloro-1′H-[2,2′;6′,2″]terpyridin-4′-one can be obtained byrecrystallisation from toluene in the form of a white crystallinepowder. ¹³C-NMR (90 MHz, CDCl₃): 165.6 (quart.); 156.5 (quart.); 154.9(quart.); 150.2 (tert.); 143.6 (quart.); 123.7 (tert.); 120.2 (tert.);108.5 (tert.).

Example 23 4,4″-Diethoxy-1′H-[2,2′;6′,2″]terpyridin-4′-one (Referred toas L17 Below)

This compound is prepared in a manner analogous to that described inExample 1, Step 2 for 1,5-di-pyridin-2-yl-pentane-1,3,5-trione, butinstead the ethoxy-substituted triketone from Example 20 is used. Pure4,4″-diethoxy-1′H-[2,2′;6′,2″]terpyridin-4′-one can be obtained bychromatography on silica gel (chloroform/methanol 9:1, 0.1% NH₄OH) inthe form of a white crystalline powder. ¹H-NMR (360 MHz, CDCl₃): 1.37(t, 6H, 7.2 Hz); 4.05 (q, 4H, 7.2 Hz); 6.77 (dd, 2H, J=5.9, 2.3 Hz),6.99 (br s, 2H), 7.30 (br s, 2H); 8.42 (d, 2H, J=5.9 Hz).

MS (EI pos., 70 eV), m/z=337 (75, [M⁺]); 322 (90); 309 (100); 281 (75);28 (85).

Example 24 4,4″-Di-pyrrolidin-1-yl-1′H-[2,2′;6′,2″]terpyridin-4′-one(Referred to as L18 Below)

This compound is prepared in a manner analogous to that described inExample 1, Step 2 for 1,5-di-pyridin-2-yl-pentane-1,3,5-trione, butinstead the pyrrolidine-substituted triketone from Example 21 is used.Pure 4,4″-di-pyrrolidin-1-yl-1′H-[2,2′;6′,2″]terpyridin-4′-one can beobtained by recrystallisation from methanol in the form of an almostcolourless solid. 1.81-2.05 (m, 8H); 3.17-3.33 (m, 8H); 6.32 (dd, 2H,J=5.7, 2.3 Hz); 6.84 (d, 2H, J=2.3 Hz); 6.90 (s, 2H); 8.19 (d, 2H, J=5.7Hz). MS (EI pos., 70 eV), m/z=387 ([M⁺]), 359 (100); 358 (85); 330 (20);28 (60).

This compound can also be obtained by heating pyrrolidine and4,4″-dichloro-1′H-[2,2′;6′,2″]-terpyridin-4′-one, if desired in thepresence of metal salts (see e.g. Example 6).

Example 254,4″-Bis[(2-hydroxy-ethyl)-methyl-amino]-1′H-[2,2′;6′,2″]terpyridin-4′-one(Referred to as L19 Below)

This compound is prepared in a manner analogous to that described inExample 6 for 4′-pyrrolidin-1-yl-[2,2′;6′,2″]terpyridine, but instead2-(N-methylamino)ethanol is used as amine and4,4″-dichloro-1′H-[2,2′;6′,2″]terpyridin-4′-one from Example 22 is usedas precursor. ¹H-NMR (360 MHz, DMSO-d6): 3.12 (s, 6H); 3.20-4.00 (m,8H); 6.73-6.82 (m, 2H); 7.70-7.95 (m, 4H); 8.23 (d, 2H, 5.9 Hz).

Example 26 4,4″-Diethoxy-4′-methoxy-[2,2′;6′,2″]terpyridine (Referred toas L20 Below)

In an argon atmosphere, 506 mg (1.5 mmol) of4,4″-diethoxy-1′H-[2,2′;6′,2″]terpyridin-4′-one (L17, Example 23) areadded at 0° C. to a suspension of 78 mg (approximately 60% dispersion inparaffin oil, 1.95 mmol) of sodium hydride in 15 ml of absoluteN,N-dimethylformamide. The mixture is then stirred for 15 minutes at 0°C. and for 15 minutes at room temperature. After cooling again, 0.12 ml(1.95 mmol) of methyl iodide is added. Stirring is then carried out atroom temperature for a further 45 minutes. 15 ml of water are added andfiltration is carried out, yielding4,4″-diethoxy-4′-methoxy-[2,2′;6′,2″]terpyridine in the form of a beigepowder. ¹H-NMR (360 MHz, CDCl₃): 1.39 (t, 6H, J=7.2 Hz); 3.90 (s, 3H);4.12 (q, 4H, J=7.2 Hz); 6.73 (dd, 2H, J=5.6, 2.5 Hz); 7.88 (s, 2H); 8.01(d, 2H, J=2.5 Hz); 8.39 (d, 2H, 5.6 Hz). MS (EI pos, 70 eV), m/z=351(90, [M⁺]); 350 (70); 336 (100); 323 (70); 295 (45).

Example 27 4′-Methoxy-4,4″-di-pyrrolidin-1-yl-[2,2′;6′,2″]terpyridine(Referred to as L21 Below)

26 mg of sodium hydride dispersion (60% strength, 0.65 mmol) aresuspended under argon in 5 ml of abs. N,N-dimethylformamide and cooledto 0° C. Then 193 mg (0.5 mmol) of4,4″-di-pyrrolidin-1-yl-1′H-[2,2′;6′,2″]terpyridin-4′-one (L18 fromExample 24) are added. The yellow suspension is stirred for 30 minutes0° C. and then heated at room temperature for 15 minutes. The mixture iscooled again and a solution of 40 μl (0.65 mmol) of methyl iodide isadded. The mixture is stirred for a further 45 minutes and theprecipitate that forms is filtered off and recrystallised from methanol.4′-Methoxy-4,4″-di-pyrrolidin-1-yl-[2,2′;6′,2″]-terpyridine is obtainedin the form of a white solid. 168.1 (quart.); 157.9 (quart.); 156.6(quart.); 152.9 (quart.); 149.5 (tert.); 107.4 (tert.); 107.1 (tert.);105.0 (tert.); 55.9 (prim.); 47.3 (sec.); 25.8 (sec.). MS (EI, 70 eV),m/z: 401 (50, [M⁺]); 373 (80); 372 (100); 332 (20); 28 (40).

Example 28 4,4′,4″-Trichloro-[2,2′;6′,2″]terpyridine (Referred to as L22Below)

This compound is prepared in a manner analogous to that described inExample 2 for 1′H-[2,2′;6′,2″]terpyridin-4′-one, but instead thedichloro-substituted pyridone L16 from Example 22 is used.4,4′,4″-Trichloro[2,2′;6′,2″]terpyridine, white solid. ¹H-NMR (90 MHz,CDCl₃): 7.24-7.31 (m, 2H), 8.38 (s, 2H); 8.45 (d, 2H, 1.8 Hz); 8.48 (d,2H, 5.0 Hz).

Example 29 4,4′,4″-Triethoxy-[2,2′;6′,2″]terpyridine (referred to as L23below)

53 mg (0.15 mmol) of 4,4′,4″-trichloro[2,2′;6′,2″]terpyridine fromExample 28 are added to 2.5 ml of a 0.72M ethanolic solution. Themixture is heated at reflux for 2 hours. The mixture is cooled, 2.5 mlof water are added and the 4,4′,4″-triethoxy[2,2′;6′,2″]terpyridine isfiltered off in the form of a pale pink powder. ¹³C-NMR (90 MHz, CDCl₃):167.4 (quart.); 166.2 (quart.); 158.4 (quart.); 157.1 (quart.); 150.7(tert.); 110.6 (tert.); 108.1 (2 signals, tert.); 64.2 (sec.); 64.1 (2signals, sec.); 15.0 (3 signals, prim.).

Example 30 4,4′,4″-Tri-pyrrolidin-1-yl[2,2′;6′,2″]terpyridine (Referredto as L24 Below)

This compound is prepared in a manner analogous to that described inExample 7 with 4′-chloro-[2,2′;6′,2″]terpyridine, but instead thetrichloro-substituted terpyridine L22 from Example 28, and pyrrolidineas amine component are used.4,4′,4″-Tri-pyrrolidin-1-yl-[2,2′;6′,2″]terpyridine, beige powder. MS(EI pos., 70 eV), m/z=440 (50, [M⁺]); 412 (80); 411 (100); 371 (20); 220(20), 28 (15). IR (cm⁻¹): 2850 (w); 1608 (vs); 1537 (s); 1515 (m); 1480(m); 1458 (m); 1019 (m); 799 (m).

Example 312-({4′,4″-Bis[(2-hydroxy-ethyl)methyl-amino]-[2,2′;6′,2″]terpyridin-4-yl}-methylamino)-ethanol(Referred to as L25 Below)

This compound is prepared in a manner analogous to that described inExample 7 with 4′-chloro-[2,2′;6′,2″]terpyridine, but instead thetrichloro-substituted terpyridine L22 from Example 28, and2-methylaminoethanol as amine component are used.2-({4′,4″-Bis[(2-hydroxy-ethyl)-methyl-amino]-[2,2′;6′,2″]terpyridin-4-yl}-methyl-amino)-ethanol,white solid. ¹³C-NMR (90 MHz, DMSO-d6): 156.4 (quart.); 155.7 (quart.);155.3 (quart.); 154.4 (quart.); 149.2 (tert.); 106.7 (tert.); 103.4(tert.); 103.1 (tert.); 58.4 (2 signals, sec.); 58.2 (sec.); 53.6(sec.); 53.5 (2 signals, sec.); 38.6 (prim.); 38.3 (2 signals, prim.).

Example 32 4′-Chloro-4,4″-diethoxy-[2,2′;6′,2″]terpyridine (Referred toas L26 Below)

This compound is prepared in a manner analogous to that described inExample 2 for 1′H-[2,2′;6′,2″]terpyridin-4′-one, but instead thediethoxy-substituted pyridone L17 from Example 23 is used.4′-Chloro-4,4″-diethoxy-[2,2′;6′,2″]terpyridine, white solid. ¹³C-NMR(90 MHz, CDCl₃): 166.3 (quart.); 157.0 (quart.); 156.9 (quart.); 150.8(tert.); 146.5 (quart.); 121.7 (tert.); 110.8 (tert.); 108.4 (tert.);64.2 (sec.); 14.9 (prim.).

Example 33 4,4″-Diethoxy-4′-pyrrolidin-1-yl-[2,2′;6′,2″]terpyridine(Referred to as L27 Below)

This compound is prepared in a manner analogous to that described inExample 7 with 4′-chloro-[2,2′;6′,2″]terpyridine, but instead thechloro-substituted terpyridine L26 from Example 32, and pyrrolidine asamine component are used.4,4″-Diethoxy-4′-pyrrolidin-1-yl-[2,2′;6′,2″]terpyridine, white solid.¹³C-NMR (90 MHz, CDCl₃): 166.2 (quart.); 159.4 (quart.); 157.1 (quart.);155.6 (quart.); 150.4 (tert.); 110.5 (tert.); 107.9 (tert.); 104.8(tert.); 63.9 (sec.); 47.8 (sec.); 25.8 (sec.); 15.0 (prim.). MS (EIpos., 70 eV), m/z=390 (100, [M⁺]); 333 (70); 305 (20); 28 (25).

Example 342-[(4,4″-Diethoxy-[2,2′;6′,2″]terpyridin-4′-yl)-(2-hydroxy-ethyl)-amino]-ethanol(Referred to as L28 Below)

This compound is prepared in a manner analogous to that described inExample 7 with 4′-chloro-[2,2′;6′,2″]terpyridine, but instead thechloro-substituted terpyridine L26 from Example 32 is used as aminecomponent. Recrystallisation from methanol yields2-[(4,4″-diethoxy-[2,2′;6′,2″]terpyridin-4′-yl)-(2-hydroxy-ethyl)-amino]-ethanolin the form of a white solid. ¹³C-NMR (90 MHz, CDCl₃): 165.5 (quart.);158.0 (quart.); 155.0 (quart.); 154.6 (quart.); 150.6 (tert.); 110.4(tert.); 107.0 (tert.); 103.5 (tert.); 63.6 (sec.); 57.9 (sec.); 52.7(sec.); 14.5 (prim.).

Example 35 6,6″-Bis(2-methoxyphenyl)-2,2′:6′:2″-terpyridine (Referred toas L29 Below)

A solution of 7.6 g (24 mmol) of caesium carbonate in 8 ml of water isadded to a solution of 0.9 g (2.3 mmol) of6′,6″-dibromo-2,2′:6′,2″-terpyridine in 14 ml of dimethoxyethane. 8.9 mg(0.02 mmol) of μ-bromo(triisopropylphosphine)(η³-allyl) palladium(II)(see WO-A-99/47474) and 0.89 g (5.88 mmol) of 2-methoxyphenylboronicacid are added. The mixture is then heated at reflux under argon for 10hours. The mixture is cooled and the phases are separated; the organicextract is extracted three times with ethyl acetate. The organic phaseis dried over sodium sulfate, filtered and concentrated. The crudeproduct is chromatographed (silica gel, hexane/ethyl acetate 10:1).6,6″-Bis(2-methoxyphenyl)-2,2′:6′:2″-terpyridine, white solid. ¹³C-NMR(90 MHz, CDCl₃): 157.7 (quart.); 155.7 (quart.); 155.3 (quart.); 138.2(tert.); 137.1 (tert.); 131.9 (tert.); 130.5 (tert.); 129.3 (quart.);125.6 (tert.); 121.6 (tert.); 121.5 (tert.); 119.5 (tert.); 112.0(tert.); 56.1 (prim.).

Example 36 6,6″-Bis(2-hydroxyphenyl)-2,2′:6′,2″-terpyridine (Referred toas L30 Below)

1.12 g (4.49 mmol) of boron tribromide dissolved in 5 ml ofdichloromethane are added dropwise at −75° C. to a solution of 200 mg(0.448 mmol) of 6,6″-bis(2-methoxyphenyl)-2,2′:6′:2″-terpyridine (L29,Example 35) in 15 ml of dichloromethane. After one hour the cooling bathis removed and the solution is stirred at room temperature for 10 hoursto complete the reaction. The solution is poured into ice-water andneutralised with sodium hydrogen carbonate solution. Extraction iscarried out twice with dichloromethane and the combined organic extractsare dried over sodium sulfate, filtered and concentrated. The crudeproduct is chromatographed (silica gel, dichloromethane/methanol 20:1).6,6″-Bis(2-hydroxyphenyl)-2,2′:6′,2″-terpyridine, white solid. ¹³C-NMR(90 MHz, CDCl₃): 160.2 (quart.); 157.7 (quart.); 154.5 (quart.); 153.1(quart.); 139.4 (tert.); 139.2 (tert.); 132.1 (tert.); 130.2 (quart.);126.9 (tert.); 121.9 (tert.); 121.6 (tert.); 120.0 (tert.); 119.5(tert.); 119.2 (tert.); 118.9 (tert.).

Synthesis of Metal Complexes with Terpyridine Ligands and 4-PyridoneLigands

Example 37 Manganese(II) Complex Containing a Pyridone Ligand:{[2,2′;6′,2″]terpyridin-4′-ol}manganese(II) chloride

198 mg (1 mmol) of manganese(II) chloride tetrahydrate are dissolved in10 ml of ethanol, and 249 mg (1 mmol) of1′H-[2,2′;6′,2″]terpyridin-4′-one L1 are added. The mixture is stirredfor 24 hours at room temperature and filtered, and the light-yellowsolid is dried in vacuo. C₁₅H₁₁Cl₂MnN₃O, 375.12; calculated C, 48.03; H,2.96; N, 11.20; Mn, 14.65. found C, 48.22; H, 3.14; N, 11.13; Mn, 14.6.IR (cm⁻¹): 3082 (br, vs), 1613 (s), 1600 (s), 1558 (s), 1429 (m), 1224(s), 1011 (m), 798 (m).

Example 38 Manganese(II) Complex with a Substituted Terpyridine Ligand:{2-[(2-hydroxy-ethyl)-[2,2′;6′,2″]terpyridin-4′-yl-amino]-ethanol}manganese(II)chloride

336 mg (1 mmol) of2-[(2-hydroxy-ethyl)-[2,2′;6′,2″]terpyridin-4′-yl-amino]-ethanol L7dissolved in 5 ml of water are added dropwise to 5 ml of an aqueoussolution of 198 mg (1 mmol) of manganese(II) chloride tetrahydrate. Themixture is then stirred for 20 minutes at room temperature and filtered,and the light-yellow solid is dried in vacuo. C₁₉H₂₀Cl₂MnN₄O₂*0.11H₂O;calculated C, 49.16; H, 4.39; N, 12.07; Mn, 11.83. found C, 49.23; H,4.38; N, 12.07; Mn, 12.1. IR (cm⁻¹): 3512 (w), 3456 (m), 1609 (vs), 1569(w), 1518 (s), 1532 (w), 1569 (w), 1473 (w), 1444 (s), 1055 (w), 1055(s), 1013 (vs), 789 (vs).

Example 38a{2-(Methyl-[2,2′;6′,2″]terpyridin-4′-yl-amino)-ethanol}manganese(II)chloride

7.66 g (25 mmol) of 2-(methyl[2,2′;6′,2″]terpyridin-4′-yl-amino)ethanolL5 are added, in five portions, over a period of 30 minutes to 100 ml ofan ethanolic manganese(II) chloride tetrahydrate solution (4.95 g, 25mmol). The mixture is diluted with 70 ml of ethanol, stirred for 18hours at room temperature and filtered, and the light-yellow solid isdried in vacuo. C₁₈H₁₈Cl₂MnN₄O; calculated C, 50.02; H, 4.20; N, 12.96;Mn, 12.71; Cl, 16.41. found C, 49.90; H, 4.12; N, 12.78; Mn, 12.9; Cl,16.33.

Example 39 Manganese(II) Complex with Two Substituted TerpyridineLigands:bis{2-[(2-hydroxy-ethyl)-[2,2′;6′,2″]terpyridin-4′-yl-amino]-ethanol}manganese(II)chloride

336 mg (1 mmol) of2-[(2-hydroxy-ethyl)-[2,2′;6′,2″]terpyridin-4′-yl-amino]-ethanol L7 aresuspended in 5 ml of ethanol/water, and an ethanolic solution of 99 mg(0.5 mmol) of manganese(II) chloride tetrahydrate is added. The mixtureis stirred at room temperature for 90 minutes and filtered, and theorange-yellow solid is dried. C₃₈H₄₀Cl₂MnN₈O₄*H₂O, calculated C, 55.89;H, 5.18; N, 13.72; Mn, 6.73. found C, 56.08; H, 5.44; N, 13.58; Mn,6.66. IR (cm⁻¹): 3240 (br), 1598 (vs), 1570 (w), 1510 (m), 1473 (m),1442 (s), 1046 (w), 1011 (vs), 792 (w).

Modification of Manganese-Bonded, Substituted Terpyridine-Like Ligands,Direct Complex Synthesis: Example 40Bis{4,4″-bis[(2-hydroxy-ethyl)-methyl-amino]-[2,2′;6′,2″]terpyridin-4′-ol}-manganese(II)chloride

318 mg (1 mmol) of L16 are heated at reflux in 25 ml of methanol with426 mg (2.2 mmol) of manganese(II) chloride tetrahydrate and 8.8 g (117mmol) of N-methylaminoethanol under argon for 18 hours. The mixture isconcentrated and the residue is chromatographed on silica gel(dichloromethane/methanol 4:1). C₄₂H₅₀Cl₂MnN₁₀O₆, yellow solid. IR(cm⁻¹): 3238 (br, m), 1603 (vs) 1511 (s), 1536 (m), 1484 (m), 1450 (m),1356 (w), 1010 (s).

Synthesis of Higher Valency Manganese Complexes with Substituted Ligandsof the Terpyridine Type (Examples 41 to 44) [cf. Process of J. Limburget al., Science 1999, 283, 1524-1527 for terpyridine]:

Example 41

1.78 g (7.14 mmol) of 1′H-[2,2′;6′,2″]terpyridin-4′-one L1 are added toa solution of 1.75 g (7.14 mmol) of manganese(II) acetate tetrahydratein 35 ml of water. Then a solution of 3.28 g (9.93 mmol of active oxygenas KHSO₅) of potassium peroxomonosulfate in 20 ml of water is addeddropwise thereto. The mixture is then stirred for 2 hours at roomtemperature, then filtered with suction and washed with 25 ml of water.Drying is carried out for 12 hours at 50° C. in vacuo, yielding 2.05 gof olive-green powder. IR (cm⁻¹): 3068 (m), 1613 (m), 1602 (m), 1587(s), 1480 (m), 1099 (vs), 1053 (w), 1028 (s), 1011 (s), 788 (m).

Example 42

1.23 g (5 mmol) of manganese(II) acetate tetrahydrate are added to asuspension of 1.68 g (5 mmol) of2-[(2-hydroxy-ethyl)-[2,2′;6′,2″]terpyridin-4′-yl-amino]-ethanol L7. Asolution of 1.44 g (4.37 mmol of active oxygen as KHSO₅) of potassiumperoxomonosulfate in 30 ml of water is then added dropwise. To theresulting red solution there is then added dropwise a total of 25 ml of1M ammonium hexafluorophosphate solution. The precipitate is filteredoff and washed twice using 10 ml of water each time. The red solid isthen taken up in 30 ml of acetonitrile, filtered through a paper filterand concentrated. The residue that remains is extracted withdichloromethane for 16 hours in a Soxhlet apparatus and then dried at50° C. in vacuo. 2.15 g of wine-red powder are obtained. IR (cm⁻¹): 2981(s), 2923 (s), 2866 (m), 2844 (m), 1621 (s), 1571 (w), 1537 (w), 1475(s), 1356 (m), 1055 (s), 1032 (vs), 1011 (s), 829 (vs), 784 (s), 740(w).

Example 43

99 mg (0.5 mmol) of manganese(II) chloride tetrahydrate are added to asuspension of 168 mg (0.5 mmol) of2-[(2-hydroxy-ethyl)-[2,2′;6′,2″]terpyridin-4′-yl-amino]-ethanol L7. Asolution of 144 mg (0.44 mmol of active oxygen as KHSO₅) of potassiumperoxomonosulfate in 3 ml of water is then added dropwise. The almostblack solid is filtered off and dried at 50° C. in vacuo. IR (cm⁻¹):3324 (br, m), 3076 (br), 1614 (s), 1523 (w), 1476 (m), 1154 (w), 1055(w), 1025 (vs), 925 (w), 647 (s).

APPLICATION EXAMPLES Application Example 1 Stability of the Mn Complexes

For this purpose, 50 μmolar aqueous solutions of a complex ofmanganese(II) chloride tetrahydrate and a terpyridine-like ligand,dissolved in a borax buffer of pH 10.0, are prepared.

For testing the stability, the solutions are exposed at 40° C. to ahydrogen peroxide concentration of 8.6 mM for 30 minutes.

For comparison purposes, a corresponding solution of the unsubstitutedterpyridine ligand is prepared (without hydrogen peroxide).

The optical density is determined by means of the respective UV/VISspectrum at the wavelength indicated in Table 1 below and is a measureof the stability.

The Mn complex of formula (137) given in Table 1 below is the compoundof formula

TABLE 1 (137)

Compound Time Optical density Unsubstituted terpyridine — 0.03 (335 nm)Mn complex (137) t = 0 min. 0.43 (335 nm) Mn complex (137) t = 30 min.(without H₂O₂) 0.11 (335 nm) Mn complex (137) t = 30 min. (with H₂O₂)0.08 (335 nm) Mn complex (134) t = 0 min. 0.60 (320 nm) Mn complex (134)t = 30 min. (without H₂O₂) 0.60 (320 nm) Mn complex (134) t = 30 min.(with H₂O₂) 0.60 (320 nm)

The above Example shows that the manganese complex with substitutedterpyridine has markedly greater stability in comparison with themanganese complex with unsubstituted terpyridine. In the case of themanganese complex with unsubstituted terpyridine, the complex haslargely decomposed after 30 minutes, and the UV/VIS spectrum obtained isvirtually the same as that of the ligand (terpyridine), whereas themanganese complex with the substituted terpyridine is stable.

Application Example 2 Bleaching Action in Washing Agents

7.5 g of white cotton fabric and 2.5 g of tea-stained cotton fabric aretreated in 80 ml of washing liquor. The liquor contains a standardwashing agent (ECE, 456 IEC) in a concentration of 7.5 g/l. The hydrogenperoxide concentration is 8.6 mmol/l. The catalyst concentration (1:1complex of manganese(II) chloride tetrahydrate with the ligand inquestion, prepared in methanolic solution with the addition of a smallamount of lithium hydroxide) is 50 μmol/l. The washing process iscarried out in a steel beaker in a LINITEST apparatus for 30 minutes at40° C. For evaluating the bleaching results, the increase in thelightness DY (difference in lightness according to CIE) of the stainsbrought about by the treatment is determined spectrophotometrically incomparison with values obtained without the addition of catalyst.

TABLE 2 1:1 Mn complex with ligand DY increase Ligand DY increase L1 5.0L10 4.4 L4 5.0 L11 5.5 L5 5.2 L17 5.3 L6 5.8 L18 3.0 L7 5.6 L19 5.3¹⁾ L85.0 L25 6.2 L8a 4.5 L28 4.3 L9 3.8 ¹⁾Half concentration used

As can be seen from Table 2 above, the manganese complexes exhibit avery good bleaching action.

Application Example 3 Cleaning Performance on Soiled Surfaces at 53° C.

A tea-stained cup is filled with 100 ml of a buffer solution (10 mMcarbonate, pH=10.0) containing 1.1 mM of hydrogen peroxide and 7.3 μM of1:1 manganese complex (prepared as described in Application Example 2).Using a thermostat, the temperature of the solution is raised from 23°to 53° C. over a period of 12 minutes and maintained at the finaltemperature for 23 minutes. After rinsing and drying in air, the resultsare evaluated visually on a scale of 1 (no cleaning) to 10 (clean). Thecatalyst-free system is used as reference.

TABLE 3 1:1 Manganese complex with ligand Rating (rating of reference)Difference L1 5.0 (3.1) 1.9 L6 7.2 (3.3) 3.9 L7 6.9 (3.3) 3.6 L10 5.2(3.1) 2.1 L11 5.7 (3.3) 2.4 L28 5.2 (3.0) 2.2 Unsubstituted 3.8 (3.9)−0.1 terpyridine

Application Example 4 Cleaning Performance on Soiled Surfaces at 23° C.

The procedure is as in Application Example 3 but the cleaning is carriedout at a constant temperature of 23° C. (duration: 45 minutes).

TABLE 4 Rating (rating of Compound used reference) Difference Manganesecomplex of formula 7.6 (3.8) 3.8 (136) N,N′-tetraacetylethylenediamine6.8 (3.9) 2.9 (TAED), 0.16 g/l

TAED is a commercially available bleach activator which is included inTable 4 for comparison purposes.

Application Example 5 Decomposition of Hydrogen Peroxide

The procedure is as in Application Example 3 but the consumption of H₂O₂is determined iodometrically.

TABLE 5 1:1 manganese complex with ligand Residual H₂O₂ (mM) Consumption(%) L1 0.73 34 Unsubstituted terpyridine 0.02 98

As can be seen in Table 5, in the case of the use of the 1:1 manganesecomplex with the substituted terpyridine ligand the undesireddecomposition of H₂O₂ to O₂ and H₂O is substantially reduced.

Application Example 6 Activity of the Manganese Catalysts After theBleaching Cycle

The procedure as described in Application Example 2 is carried out forthe 1^(st) cycle, the cotton fabric is removed and for the 2^(nd) cyclethe procedure is carried out afresh with a new, as yet untreated cottonfabric. The DY values are determined as described in Application Example2.

TABLE 6 Bleaching value Bleaching with H₂O₂ value with H₂O₂ and the 1:1Mn (without complex with Difference Mn complex) the ligand L7 DDY 1^(st)cycle DY = 14.9 DY = 23.0 8.1 2^(nd) cycle DY = 11 DY = 19.0 8.0

As can be seen from Table 6, the liquors comprising the manganesecomplex can be used for further bleaching cycles without any appreciablereduction in the bleaching action.

Application Example 7 Catalytic Bleaching of Cellulose

20 g of cellulose [TPP-CT CSF129, Ref. No. P-178635 (ISO 57.4)] aresteeped in a litre of water for 65 hours and then stirred in a mixer for2 minutes to give a paste-like pulp. A bleaching bath containing 50 g ofthe pulp so prepared in 180 ml of water, 100 μM of Dequest 2041(sequestering agent), 8.6 mM of hydrogen peroxide and 20 μM of catalystfrom Example 35 is maintained at 40° C. for 30 minutes. At the same time1N sodium hydroxide solution is metered-in in such a manner that a pH of10.0 is maintained. Filtration and air-drying are then carried out. Asample that has been compressed to form a circular sheet of 10 cmdiameter is then tested for the lightness Y obtained (according to CIE,reflectance spectroscopy). The results are compiled in the followingTable.

TABLE 7 Lightness Y Test sample, untreated 63.4 Test sample,catalytically bleached 66.9

Application Example 8 Action as Catalyst for DTI (Dye TransferInhibition)

In accordance with this application, the redeposition of dyes in washingliquors, especially, should be avoided.

7.5 g of white cotton fabric are treated in 80 ml of washing liquor. Theliquor contains a standard washing agent (ECE, 456 IEC) in aconcentration of 7.5 g/l. The hydrogen peroxide concentration is 8.6mmol/l. The catalyst concentration (of manganese(II) chloridetetrahydrate with the ligand, prepared in methanolic solution with theaddition of a small amount of lithium hydroxide) is 50 μmol/l, and asolution of the test dye Direct Brown 172 having 10 mg/l of the 250%formulation. The washing process is carried out in a steel beaker in aLINITEST apparatus for 30 minutes at 40° C. For testing the activity ofthe catalysts, the DTI activity is determined. The DTI (Dye TransferInhibition) activity a is defined as the following percentage.

a=([Y(E)−Y(A)]/[Y(W)−Y(A)])*100

where Y(W), Y(A) and Y(E) are the CIE lightness values of the whitematerial, of the material treated without the addition of catalyst andof the material treated with the addition of catalyst, in that order.a=0 denotes a completely inactive product, the addition of which to thewashing liquor does not prevent dye transfer, whereas a=100% correspondsto a perfect catalyst which totally prevents the staining of the whitematerial.

The reflection spectra of the samples were measured using a SPECTRAFLASH2000 and converted into lightness values (D65/10) in accordance with astandard CIE procedure.

A 1:1 manganese complex with ligand L7 gives a value of a=90% inaccordance with the test procedure described above.

Application Example 9

The use of the catalysts according to the invention causes hardly anyadditional fading of the dyes in dyed cotton laundry. When used asdescribed above in Application Example 8, after treatment five times, onaverage, virtually no losses of dye are recorded. The values given inthe following Table are relative percentage dye losses, determined onthe basis of Kubelka-Munk values at the respective absorption maximum.

TABLE 8 Dye loss (%) in system Cotton dyeing with dye with Mn-L7 (50 μM)without catalyst Cibanone Brown BR 0 0 Cibanone Blue RS 3 2 ProcionBrown H-4RD 9 11 Levafix Scarlet E-2GA 10 10

Application Example 10 Catalytic Action for the Epoxidation of Olefins

17 mg (0.05 mmol) of2-[(2-hydroxy-ethyl)-[2,2′;6′,2″]terpyridin-4′-yl-amino]-ethanol (L7,Example 7), 10 mg (0.04 mmol) of manganese(II) acetate tetrahydrate and0.32 mmol of sodium ascorbate are added to a solution of 1.09 ml (10mmol) of ethyl acrylate in 0.5 ml of acetonitrile. The mixture is cooledin an ice bath and a 30% strength hydrogen peroxide solution (2.27 g, 20mmol) is added dropwise thereto in the course of 20 minutes. The mixtureis then left for 14 hours at room temperature, then diluted with diethylether and the phases are separated. The organic extract is dried oversodium sulfate, filtered and concentrated. The catalytic turnover numberfor the epoxide formed, ethyl oxirane-2-carboxylate, is determined bycomparing the intensity of the epoxide methine proton at 3.34-3.38 ppmwith the ligand signal L7 at 8.53 ppm as reference and is 35±8. Ethyloxirane-2-carboxylate, epoxide signals ¹H-NMR (360 MHz, CDCl₃):2.68-2.89 (m, 2H, CH₂); 3.34-3.38 (m, 1H, CH). Without the addition ofligand, epoxide cannot be detected.

(see in this connection also Berkessel, A. et al., Tetrahedron Lett.1999, 40, 7965-7968).

1. A metal complex compound of formula[L_(n)Me_(m)X_(p)]^(z)Y_(q)  (1a), wherein Me is manganese, titanium,iron, cobalt, nickel or copper, X is CH₃CN, H₂O, F⁻, Cl⁻, Br⁻, HOO⁻, O₂²⁻, O²⁻, R₁₇COO⁻, R₁₇O⁻, LMeO⁻ or LMeOO⁻ wherein R₁₇ is hydrogen orunsubstituted C₁-C₁₈alkyl or aryl; or R₁₇ is C₁-C₁₈alkyl substituted byhydroxyl, C₁-C₄ alkoxy, sulfo, or sulfato; or R₁₇ is aryl substituted byC₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl, sulfo,hydroxyl, amino, N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted orsubstituted by hydroxy in the alkyl moiety, N-phenylamino,N-naphthylamino, phenyl, phenoxy or by naphthoxy; n and m are eachindependently of the other an integer having a value of from 1 to 8, pis an integer having a value from 0 to 32, z is the charge of the metalcomplex, Y is a counter-ion, q=z/(charge Y), and L is a ligand offormula

wherein R₆ is —NR₁₄R₁₅ or —N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄ and R₁₅ togetherwith the nitrogen atom bonding them form an unsubstituted or substituted5-, 6- or 7-membered ring which may optionally contain further heteroatoms; R₁₆ is independently of the other(s) hydrogen or unsubstitutedC₁-C₁₈alkyl or aryl; or R₁₆ is C₁-C₁₈alkyl substituted by hydroxyl,C₁-C₄ alkoxy, sulfo, or sulfato; or R₁₆ is aryl substituted byC₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl, sulfo,hydroxyl, amino, N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted orsubstituted by hydroxy in the alkyl moiety, N-phenylamino,N-naphthylamino, phenyl, phenoxy or by naphthoxy; and R₁, R₂, R₃, R₄,R₅, R₇, R₈, R₉, R₁₀ and R₁₁ are each independently of the others asdefined above for R₆ or are hydrogen or unsubstituted aryl; or R₁, R₂,R₃, R₄, R₅, R₇, R₈, R₉, R₁₀ and R₁₁ are aryl substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl, sulfo, hydroxyl, amino,N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or substituted byhydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, phenyl,phenoxy or by naphthoxy; or R₁, R₂, R₃, R₄, R₅, R₇, R₈, R₉, R₁₀ and R₁₁are unsubstituted C₁-C₁₈alkyl; cyano; halogen; nitro; —COOR₁₂ or —SO₃R₁₂wherein R₁₂ is in each case hydrogen, a cation or unsubstitutedC₁-C₁₈alkyl or aryl; —SR₁₃, —SO₂R₁₃ or —OR₁₃ wherein R₁₃ is in each casehydrogen or unsubstituted C₁-C₁₈alkyl or aryl; —N(R₁₃)—NR′₁₃R″₁₃ whereinR₁₃, R′₁₃ and R″₁₃ are as defined above for R₁₃; —NR₁₄R₁₅ or—N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are each independently of theother(s) hydrogen or unsubstituted C₁-C₁₈alkyl or aryl; wherein R₁₂,R₁₃, R₁₄, R₁₅, and/or R₁₆ each independently of the others as definedabove or are C₁-C₁₈alkyl substituted by hydroxyl, C₁-C₄ alkoxy, sulfo,or sulfato; R₁₂, R₁₃, R₁₄, R₁₅, and/or R₁₆ each independently of theothers as defined above or are aryl substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl, sulfo, hydroxyl, amino,N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or substituted byhydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, phenyl,phenoxy or by naphthoxy; and with the proviso that when Me is titanium,iron, cobalt, nickel or copper, R₃ and R₉ are not hydrogen and the threeradicals R₃, R₆ and R₉ do not have identical meanings.
 2. A metalcomplex compound according to claim 1, wherein Me is manganese which ispresent in oxidation state II, III, IV or V.
 3. A metal complex compoundaccording to claim 1, wherein the ligand is a compound of formula

wherein R₁₆ is —NR₁₄R₁₅ or —N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄ and R₁₅ togetherwith the nitrogen atom bonding them form an unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring; and R′₃ and R′₉ are as defined above for R′₆ or arehydrogen or phenyl unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl, sulfo, hydroxyl, amino,N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or substituted byhydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, phenyl,phenoxy or by naphthoxy; or R₁₃ and R′₉ are C₁-C₁₂alkyl; cyano; halogen;nitro; —COOR₁₂ or —SO₃R₁₂ wherein R₁₂ is in each case hydrogen, acation, C₁-C₁₂alkyl, or phenyl unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano, nitro, carboxyl, sulfo,hydroxyl, amino, N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted orsubstituted by hydroxy in the alkyl moiety, N-phenylamino,N-naphthylamino, phenyl, phenoxy or by naphthoxy; —SR₁₃, —SO₂R₁₃ or—OR₁₃ wherein R₁₃ is in each case hydrogen, C₁-C₁₂alkyl, or phenylunsubstituted or substituted as indicated above; —N(R₁₃)—NR′₁₃R″₁₃wherein R₁₃, R′₁₃ and R″₁₃ are as defined above for R₁₃; —NR₁₄R₁₅ or—N^(⊕)R₁₄R₁₅R₁₆ wherein R₁₄, R₁₅ and R₁₆ are each independently of theother(s) hydrogen, unsubstituted or hydroxyl-substituted C₁-C₁₂alkyl, orphenyl unsubstituted or substituted as indicated above.